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By Mark J. Klein, Robert A. Haggins

The pesence of a small amount of oxygen was found to cause significant grain growth restraint in 99.99 pct Ag. This behavior does not seem to be due to the presence of an oxide dispersion, but instead, to be related to the existence of minute amounts of oxygen m solid solution. In the amounts necessary to cause the observed effects it was found that oxygen migrates with extreme rapidity, probably along extended structural imperfections, such as dislocations and grain boundaries. A number of years ago, hastton' observed that the presence of small amounts of oxygen caused a retardation of grain growth in silver. He attributed this behavior to the formation of a fine dispersion of oxide particles by the internal oxidation of trace impurities. More recently, wood2 also found that oxygen caused grain growth restraint in copper. Experiments using both copper and a dilute solution of aluminum in copper led to the conclusion that the effects observed in copper were due to oxygen in solid solution, rather than an oxide dispersion. During the course of a study of the influence of several solutes on the recrystallization of Silver, the presence of minute amounts of oxygen was found to exert a very significant influence on grain growth. The experiments reported here were undertaken to determine whether the grain growth restraint observed in silver due to the presence of oxygen is related to oxygen in solution or to an oxide dispersion. Because of the difficulty in measurement and control of the very small oxygen concentrations causing the observed effects no attempt was made to treat the data in a quantitative manner. EXPERIMENTAL PROCEDURE AND RESULTS Silver of 99.99 pct purity was melted and cast into slabs in a vacuum of better than 0.1 p. These slabs were reduced 50 pct by cold rolling to a thickness of approximately 2.5 mm. Samples cut from this material were annealed in vacuum for a series of different times at 803°C. Another group of samples was similarly annealed in air. This temperature is well above the recrystallization range for silver of this purity (150" to 200°C). The mean grain diameter of these samples was measured, both in the center and near the edge, using the line-intel-cept method, and is shown as a function of annealing time in Fig. 1. The grain size in the centers of the samples annealed in air was found to be larger than that of the surface regions, while the grain growth behavior of the edge and center regions annealed in a vacuum was approximately the same. he edge measurements were taken at a distance of 0.2 mm from the surface.) A few samples were annealed in nitrogen. Their behavior was identical to that of the vacuum-annealed samples. Samples annealed in oxygen had approximately the same grain growth behavior as those annealed in air, leading to the conclusion that this behaviouer is due to oxygen. The microstructure of a sample annealed in air at 803" for. 30 minutes is shown in Fig. 2. The smaller grain size near the surface is characteristic of the iir-annealed specimens. Possible causes of this grain growth restraint in the air-annealed specimen are the formation of an im-

Jan 1, 1962

By R. A. Generes, H. C. H. Darley

Laboratory tests showed that at elevated temperatures a reaction takes place between all metal hydroxides and clay muds, which results in a thickening or solidifying of the mud, the extent of which depends on the nature of the ingredients. Calcium hydroxide gave the strongest solidification whereas barium hydroxide only caused a mild thickening, indicating that the use of barium hydroxide muds instead of lime muds would be a good way of preventing high-temperature solidification. It was found possible to prepare barium mud in the laboratory with caustic soda and a thinner in the same manner as lime muds, and these barium muds had the same or better toleration of high solids content, resistance to salt contamination, and low gel strengths as the corresponding lime muds. Three field trials have been made with barium mud. The principal difficulty encountered was in determining the correct proportions of the tourly treatments required to maintain low gel strengths. A satisfactory systern was finally developed, and low gels were maintained throughout the third test. The wells on which the trials were made were not carried deep enough to test the resistance to solidification adequately, but oven tests at 350°F were made periodically and no tendency to solidification was noted except immediately after severe cernent contamination had introduced excessive amounts of calcium into the system. Although barium hydroxide costs considerably more than lime, the total mud costs were as low, and on the last well significantly lower, than the average cost of lime mud wells drilled in the vicinity. INTRODUCTION The advantages of repressing dispersion and hydra-tion of clay cuttings carried in the mud, particularly when drilling through thick clay formations, are well recognized. This repression is generally achieved by the use of lime, and lime muds have in consequence the desirable characteristics of high toleration of solids, low thixotropy, and good resistance to contamination. They have, however, the disadvantage of high-temperature solidification. This phenomenon has been described in detail by Gray et al, who have shown that it is the result of a chemical reaction between the hydroxides and the clay minerals. The work described in this paper was undertaken to find a substitute for lime which would not cause this solidification. LABORATORY EXPERlMENTS The principal positive requirement for a substitute for lime is that it should repress the hydration and dispersion of clay. It is well known that monovalent cations promote hydration while polyvalent cations repress it. Therefore, a few representative polyvalent salts and hydroxides were tested to determine whether they could be used as substitutes for lime. Their efficiency at repressing hydration and dispersion was measured by means of the clay-volume test. It has been shown elsewhere' that this test is a good measure of degree of dispersion of clay in suspension and that hydration accompanies and correlates with dispersion, so that measuring one measures the other. The test is made by centrifuging a 1:100 mixture of mud and 1-N NaCl and observing the volume of sediment—the greater the volume, the greater the dispersion. The tendency to caux solidification was measured by heating the muds in pressure vessels for 16 hours at 150°F and 370°F. An approximate quantitative

Jan 1, 1957

LANS are underway for the annual meeting of AIME, to be held in New York, February 17 to 21. The technical program includes meetings of all divisions of all three branches, Mining, Metals, and Petroleum. The bulk of the technical sessions will be held at the Statler Hotel, and the annual banquet will be held at the Waldorf-Astoria, Wednesday evening, February 20. The technical program of the Mining Branch activities is included in this issue. While it is not complete in every detail, it shows general interest groupings as well as subjects to be discussed. The program for each division is shown separately to facilitate following the activities of these special interest groups. Then, after a full scale and possibly somewhat strenuous technical meeting, a post-meeting feature will appeal to many of the members. A restful cruise to Bermuda and Nassau is offered at special rates to AIME members and friends. The schedule is a 3:00 pm departure from New York on the Queen of Bermuda on Saturday, February 23; arrival at Bermuda at 7:00 am Monday, February 25; arrival at Nassau at noon, Wednesday, February 27; and the trip ending again in New York at 9:00 am, Saturday, March 1. Rates begin at $202.10 per person, with higher rates depending upon accomodations desired. The base rate includes outside room with private bath and all meals, as well as Federal, Bermuda and Nassau taxes. Reservations for the trip should be made immediately through Leon V. Arnold, 36 Washington Square West, New York 11, who is in charge of arrangements.

Jan 1, 1952

By Howard Scott

The great advances made in mechanical engineering during recent years through the use of alloy steels, as illustrated by the development of the airplane and automobile, may be ascribed primarily to the application of nickel as an alloying element. The ternary system iron-carbon-nickel has a wide industrial application and forms, further, thefundamental basis of the even greater class of the widely used quarternary steels such as nickel-chromium, nickel-silicon, and nickel-vanadium. As is not uncommon with such cases of virile growth in an industry, the application of the alloy steel in a largely empirical manner has outstripped its scientific development so that a fertile field for metallographic research still remains. In this field, the basic nickel steels require first consideration and are the subject of the present investigation, which is offered as a preliminary to the study of the more complex alloys of industrial importance Of the principal tools of metallography—microscopic examination, determination of mechanical properties, and thermal analysis—the last has developed much more slowly in its application to industrial needs so that the situation often exists that heat treatment operations are based on empirically determined temperatures; that is, temperatures deterrnincd without regard to the actual transformation characteristics of the alloy. This situation is undesirable as there is no uniform standard for comparison of results. It is due, outside the usual difficulties involved in temperature measurements, to the pioneer character of much of the published work; to the lack of definiteness of the Ac, transformation,1 particularly in low-carbon steels; to the failure to define operating conditions completely; and to the paucity of information correlating thermal characteristics with results of heat treatment.

Jan 1, 1922

By Howard Scott

The great advances made in mechanical engineering during recent years through the use of alloy steels, as illustrated by the development of the airplane and automobile, may be ascribed primarily to the application of nickel as an alloying element. The ternary system iron-carbon-nickel has a wide industrial application and forms, further, thefundamental basis of the even greater class of the widely used quarternary steels such as nickel-chromium, nickel-silicon, and nickel-vanadium. As is not uncommon with such cases of virile growth in an industry, the application of the alloy steel in a largely empirical manner has outstripped its scientific development so that a fertile field for metallographic research still remains. In this field, the basic nickel steels require first consideration and are the subject of the present investigation, which is offered as a preliminary to the study of the more complex alloys of industrial importance Of the principal tools of metallography—microscopic examination, determination of mechanical properties, and thermal analysis—the last has developed much more slowly in its application to industrial needs so that the situation often exists that heat treatment operations are based on empirically determined temperatures; that is, temperatures deterrnincd without regard to the actual transformation characteristics of the alloy. This situation is undesirable as there is no uniform standard for comparison of results. It is due, outside the usual difficulties involved in temperature measurements, to the pioneer character of much of the published work; to the lack of definiteness of the Ac, transformation,1 particularly in low-carbon steels; to the failure to define operating conditions completely; and to the paucity of information correlating thermal characteristics with results of heat treatment.

Jan 1, 1922

By Sanford S. Cole

LABORATORY TESTS Takakuwa and Takamori' have applied the principle of phase inversion, well known in the chemistry of colloids, as a means of evaluating the wettability of minerals and to classify some frothing agents. By determining the angle of contact across the liquid phase of an emulsion, it has been possible to readily determine the wettability of a mineral. When this angle is less than 90°, the emulsion is of the oil-water type, and if it is greater than 90a, then the emulsion is of the water-oil type. The authors replaced oil with benzene in their recommended operation. They studied this method with the influence of ethyl xanthene on galena, on activated or unactivated zinc blend and of sodium cyanide on chalcopyrite and zinc blend. Raffinot and Formanek" described a pilot flotation plant with a capacity of 33 to 66 lb per hr of ore which is at the Laboratory of the Sociktk Minerais et Metaux in Paris. The plant will handle about 440 lb of ore per 8-hr shift and a regular series of tests can be undertaken with two to three tons of ore. Ore is ground to 0.1 in. and blended in advance. The plant includes two mills used either as rod mills or ball mills, conditioners, four groups of three cells for rougher circuits, eight cleaner cells and two small mills for regrinding middlings. Automatic controls for the pulp level in the cells, automatic sampling and addition of flotation reagents by electric valves facilitate plant operation and help to produce regular runs in spite of small throughputs.

Jan 8, 1963

By A. G. H. Anderson, Eric R. Jette

A few years ago, while the writers worked on the constitution of ternary and quaternary alloys consisting mainly of iron, chromium and siliconl,2 some information on microstructures and hardness, not incorporated in the published work, alas obtained. It has not been possible to do any further work on the properties of the alloys. The information possessed is hereby presented for the interest it may have in connection with the constitution of the alloys. Microstructures Referring to the iron-chromium-silicon diagram,' the regions that received most attention were those in which the sigma phase appears. It was found that the mode of occurrence of this phase varied much with the condition under which it mas formed, and the mode influenced considerably the hardness of the alloys. In some slowly cooled alloys, well within the alpha + sigma-phase boundary, sigma occurs in pabterns suggesting a eutectic. The structure of such an alloy is shorn in Fig. 1, showing it to be partly coarsely laminated and partly globular mottled. In other annealed and slowly cooled alloys, the lanlinated structure is entirely absent, and sigma appears in an irregular distribution of sharply cornered elongated areas (Figs. 2 and 3). These areas all possess a more or less mottled structure. A carbide phase is also visible in these two photomicrographs; it is represented by bright white arras of various shapes, sometimes apparently enveloping the sigma. Quenched and aged specimens, whose compositions arc: located near the phase boundary between alpha and sigma + alpha regions, have structures not unlike martensite (Figs. 5 and 6). Fig. 4 shows the structurc of alloy No. 35 as quenched from 1100" C.; it is a typical solid solu-

Jan 1, 1938

By Eric R. Jette, A. G. H. Anderson

A few years ago, while the writers worked on the constitution of ternary and quaternary alloys consisting mainly of iron, chromium and siliconl,2 some information on microstructures and hardness, not incorporated in the published work, alas obtained. It has not been possible to do any further work on the properties of the alloys. The information possessed is hereby presented for the interest it may have in connection with the constitution of the alloys. Microstructures Referring to the iron-chromium-silicon diagram,' the regions that received most attention were those in which the sigma phase appears. It was found that the mode of occurrence of this phase varied much with the condition under which it mas formed, and the mode influenced considerably the hardness of the alloys. In some slowly cooled alloys, well within the alpha + sigma-phase boundary, sigma occurs in pabterns suggesting a eutectic. The structure of such an alloy is shorn in Fig. 1, showing it to be partly coarsely laminated and partly globular mottled. In other annealed and slowly cooled alloys, the lanlinated structure is entirely absent, and sigma appears in an irregular distribution of sharply cornered elongated areas (Figs. 2 and 3). These areas all possess a more or less mottled structure. A carbide phase is also visible in these two photomicrographs; it is represented by bright white arras of various shapes, sometimes apparently enveloping the sigma. Quenched and aged specimens, whose compositions arc: located near the phase boundary between alpha and sigma + alpha regions, have structures not unlike martensite (Figs. 5 and 6). Fig. 4 shows the structurc of alloy No. 35 as quenched from 1100" C.; it is a typical solid solu-

Jan 1, 1938

By J. M. Gaines, C. H. Herty

IRon oxide (FeO) plays an extremely important part in the manufacture of steel. In the open-hearth furnace and the Bessemer converter it is the chemically predominant compound and controls to a large extent both the operation of the furnaces and the composition and quality of their products. Almost all of the refining action is carried out through the medium of FeO, which oxidizes carbon, manganese, silicon and phosphorus. At the end of any open-hearth or Bessemer heat the steel contains dissolved iron oxide, which must be wholly or partly eliminated. The type of deoxidation product depends on the amount of dissolved iron oxide and on the deoxidizer used. After the heat has been deoxidized and while it is being teemed, iron oxide diffuses from the ladle slag into the metal, causing losses of deoxidizer and increase in iron oxide content of the steel. It is generally believed that non-metallic inclusions are responsible for a great many failures of steel in service and for decreased yield of steel during rolling. The basis of most non-metallic inclusions is dissolved iron oxide. This investigation was undertaken in order to determine the amount of iron oxide that will dissolve in iron under various conditions. Steel-making slags are complex and it has been thought best to determine solubility under simple slags as a first step. The study is being continued under slags whose compositions approach those of operating slags Previous Investigations The solubility of oxygen in iron has been determined by a number of investigators (see Table 1) but their effort's have been directed toward the

By R. Fahn

Bentonites are best suited for the preparation of acid activated clays with efficient adsorption properties. They are weathering products of acid volcanic ashes and natural deposits are spread worldwide. The main constituent of bentonite is aluminum hydrosilicate montmorillonite with a high ability to swell. Physical and Chemical Properties of Montmorillonite The clay mineral montmorillonite is named after its place of discovery, near Montmorillon in southern France. The structure of this clay is shown in [Fig. 1]. The montmorillonite crystal consists of about 15-20 silicate plates. Each silicate plate is composed of three layers. The central one is formed by aluminum or by ferric hydrate octahedrons, the two outer ones consist of silicon dioxide tetrahedrons. In the presence of water, the montmorillonite crystal swells and water molecules become deposited between individual silicate layers. Two types of natural bentonites are known: the Western type, which is a natural sodium bentonite (high swelling grade), and the Southern type, an alkaline earth or calcium bentonite (low swelling grade). Southern bentonites have efficient adsorption properties of their own. They are called natural active earths or fullers earths. Acid Treatment of Bentonite Under the influence of a mineral acid, the exchangeable alkaline earth ions of bentonite are substituted by hydrogen ions. Moreover, depending on the acid concentration, temperature, pressure, and reaction time, a more or less pronounced leaching process takes place. Thereby Al-, Fe-, and Mg-ions are extracted from the octahedron layers. This results in a change in the crystalline structure of montmorillonite and in an increase of its specific surface area and porosity, as shown in [Fig. 2].

Jan 1, 1983

By D. P. Kedzie, R. A. Dodd

The fatigue strength, fatigue hardening, and effect of fatigue deformation on subsequent age hardening of supersaturated Al(Cu) solid solutions have been determined as functions of alloy composition and temperature. The fatigue strength/tensile strength ratios, determined at 150°, 25°, and -195°C, decreased with increase in alloy content for all temperatures, but the F.S./U.T.S. ratios at -195°C decreased much more rapidly than did the ratios for 150" and 25°C. This suggested that strain aging and/or age hardening occurred during tests at higher temperatures. Additionally, the F.S./U.T.S. ratios at 150°C exceeded those at 25°C for all compositions, indicating greater strengthening during fatigue at 150°C. The effect of fatigue or tensile deformation at 150°, 25°, and -195°C on subsequent age hardening showed that the deformatzon increased the rate of precipitation and indicated that mechanically produced vacancies were probably formed during deformation. Fatigue hardening was studied at 150°, 25°, and -195°C, and the effect of room-temperature rests after 10 and 100 cycles was examined. The results confirmed that strain aging occurred at the higher temperatures . DURING the last 15 years various mechanisms of fatigue crack nucleation and growth based on dislocation and vacancy interactions, operating singly or collectively, have been proposed. The probable consensus of present opinion is that the fatigue process in pure metals essentially involves dislocation interactions, and that vacancies formed by such interactions play a minor or inconsequential role. However, there is some evidence that age-hardened alloys tend to overage during fatigue, probably by local vacancy-enhanced diffusion, and strain aging also might be important in selected cases. Furthermore, it has been established that the behavior of quenched-in vacancies in Al(Cu) and other solid solutions is composition-sensitive. Therefore, it seemed worthwhile to investigate various aspects of the fatigue behavior of supersaturated Al(Cu) alloys and to examine the results in terms of vacancy-enhanced effects. EXPERIMENTAL The alloys used in this investigation were prepared from 99.994 wt pet A1 and OFHC copper, the latter containing 0.04 pet 0 as the principal impurity. Six alloys were made, containing, by actual analysis, 0.58, 0.96, 1.96, 2.85, 4.45, and 5.51 wt pet Cu. They were induction-melted in air in graphite crucibles, cast as 7-in. by 7/8-in.-diam rods in graphite molds, and hot-rolled to 5/8 in. diam. The experimental work was a three-part program involving the determination of a) 10' cycle fatigue stresses as a function of alloy composition and temperature; b) the effect of fatigue deformation on subsequent aging of the supersaturated alloys; and c) fatigue hardening as a function of alloy composition and temperature. For determining the 105 cycle fatigue stresses, a portion of the 5/8-in. stock was machined into Krouse rotating cantilever beam fatigue specimens, 2 in. in length by 1/4 in. minimum diameter. These were tested at +150°, 25°, and -195°C (liquid nitrogen) on a Krouse high-speed machine, with special weights to provide lower -than-normal loading ranges, this being necessitated by the small load requirements of those alloys of lower copper content. For the high-temperature tests a small resistance heater was designed to clear the collets and fit in between the chucks, while for the low-temperature tests a hollow nylon cylinder was used, having closed ends drilled to pass a fatigue specimen, and positioned similarly to the heater. A plexiglass container completely enclosed the fatigue machine; rubber gloves fixed to ports in the walls enabled the machine to be operated from outside the box. A tray of magnesium perchlorate dried the air in the container and prevented both atmospheric corrosion fatigue at room and elevated temperatures and troublesome ice build-up at low temperatures. A total of ten to fifteen specimens was used for each combination of alloy composition and temperature. The result of each test was plotted on a standard S-N diagram, and the next stress was selected on the basis of the trends indicated by previous specimens. In this manner a small portion of the S-N diagram was constructed, and the 105 cycle fatigue stress obtained. Small Krouse fatigue specimens were also used to study the effect of cyclic prestrain on subsequent

Jan 1, 1964

By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01' and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-' cm-'). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-' cm-'). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

By Howard L. Hartman

Probably no aspect of underground excavation is as important or as neglected as the environment. The Committee on Rapid Excavation, formed by the National Academy of Engineering to study the technological needs for "rapid" underground excavation in tunnels, shafts, and mines of the future, encountered a blank wall in attempting to evaluate environmental needs. In fact, so little quantitative information on the extent of present-day hazards is available that projection of future environmental-control demands must await more adequate assessment of current hazard levels. Further, there are not even accepted tolerance standards for many environmental conditions, such as heat, noise, and illumination. Only certain atmospheric contaminants have been satisfactorily catalogued. Any technical study, therefore, which purports to examine the state-of- the-art on underground environmental control must, in reality, settle for a cursory survey of a rather nebulous subject. ENVIRONMENTAL HAZARDS To contend adequately with hazards in the underground environment requires some knowledge of their nature and characteristics. In this regard, it is helpful first to identify our concern: when, where, and to whom or what may environmental conditions constitute "hazards"? Table 1 summarizes considerations that are important in this regard. For the purposes of this Conference (and book), primarily directed toward the excavation process itself, the hazards of consequence occur during excavation (item A) and primarily within the excavation (item B). However, some attention must be given to external hazards as well, since these may affect excavation. The object of concern (item C) is mainly human safety, although property security is also important. Hazards occur in a variety of forms. If one is to devise suitable control

Jan 1, 1970

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a' phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a' platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a' phase in titanium binary alloys.' In the Ti-Mo system,' two modes of a' decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a', and the other involves diffusion across the a'-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a' along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a' phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a' over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a' structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a' are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a' peaks broadened during the initial stages of tem-

Jan 1, 1965

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg's limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950

PLANS are underway for the annual meeting of AIME, to be held in New York, February 17 to 21. The technical program includes meetings of all divisions of all three branches, Mining, Metals, and Petroleum. The bulk of the technical sessions will be held at the Statler Hotel, and the annual banquet will be held at the Waldorf-Astoria, Wednesday evening, February 20. The technical program of the Mining Branch activities is included in this issue. While it is not complete in every detail, it shows general interest groupings as well as subjects to be discussed. The program for each division is shown separately to facilitate following the activities of these special interest groups. Then, after a full scale and possibly somewhat strenuous technical meeting, a post-meeting feature will appeal to many of the members. A restful cruise to Bermuda and Nassau is offered at special rates to AIME members and friends. The schedule is a 3:00 pm departure from New York on the Queen of Bermuda on Saturday, February 23; arrival at Bermuda at 7:00 am Monday, February 25; arrival at Nassau at noon, Wednesday, February 27; and the trip ending again in New York at 9:00 am, Saturday, March 1. Rates begin at $202.10 per person, with higher rates depending upon accomodations desired. The base rate includes outside room with private bath and all meals, as well as Federal, Bermuda and Nassau taxes. Reservations for the trip should be made immediately through Leon V. Arnold, 36 Washington Square West, New York 11, who is in charge of arrangements.

Jan 1, 1952

By William P. Blake

The mineral, garnet, is a common associate of copper-ore in the southwestern portion of the United States. This association may be observed on a large scale in southwestern Arizona, in southern New Mexico and in Sonora, Old Mexico, especially at El Cananea, and at Nacozari. At other localities in Mexico the general occurrence of garnet " as a contact metamorphic mineral" in the copper-deposits of the Cretaceous limestone is noted by José G. Aguilera.1 It is usually found at the contact of this limestone with diorites, granites, etc., at numerous mines. The same authority also cites the occurrence of garnet in metamorphosed Cretaceous limestone alongside of diorite dikes in association with iron-ore. Other foreign examples are found in the Banat and Servia, at Rezbanya in Hungary, and Offenbanya in Transylvania, and at Bogoslovsk in the Urals. In New South Wales, at Broken Hill, the gangue in the Proprietary mine is chiefly garnet, with quartz, opal and rhodonite.2 Also, in a recent paper by George Smith, entitled, " The Garnet-Formations of the Chillagoe Copper-Field, North Queensland, Australia,"3 it is shown that in the copper-field of Chillagoe, Australia, where there are many lode-formations, about one-half of the number are garnetiferous, and many of this garnet-type are associated with magnetite, which is regarded as of analogous origin. The two minerals are found merging imperceptibly into each other. These examples suffice to show the very general and wide distribution of garnet as an associate of copper-ore. In addition to the localities already mentioned as known in Arizona may be mentioned the copper-mines and occurrences

Jan 1, 1904

By J. M. Gaines, C. H. Herty

It is a matter of frequent record in the literature that manganese will desulfurize molten iron under proper conditions. Particularly has much been written with regard to this action in the mixer, and numerous reports have been published describing experiments in which advantage was taken of this phenomenon in order to obtain a purer iron for the open hearth. The question of sulfur elimination in the ladle has, however, received comparatively little attention. The reaction by which sulfur is removed is considered to be: FeS + Mn = MnS + Fe. The manganese sulfide, being but sparingly soluble in the iron, and of a lower density, will rise from the body of the metal and collect as a slag on the surface. It is therefore an action taking place solely in the metal, and independent of interaction between slag and metal. As will be shown later the presence of slag on the metal tends to offset the effect of manganese elimination. It is this fact which distinguishes desulfuriza-tion in the ladle from desulfurization in the mixer, for it has been shown1 that the amount of sulfur eliminated in the mixer is closely tied up with the composition of the slag. Experimental Procedure In order to ascertain the extent of and the factors controlling this elimination in the ladle, several casts were sampled carefully at the blast furnace and again when the ladles were being emptied, either at the mixer, open hearth, or foundry. If the sulfur content varied from ladle to ladle at the blast furnace the average sulfur content of each ladle was obtained by integrating the curve "sulfur vs. time " for the cast under

Jan 1, 1927

By R. S. Dean

True careful work of Gross and Zimmerley1 has established the fact that the energy actually used in grinding is proportional to the new sur-face produced. This confirmation of Rittinger's law was made by crush-ing quartz in a frictionless drop-weight machine and determining the surface of the quartz by its rate of solution in hydrofluoric acid. The details of this procedure have been described adequately elsewhere and need not be repeated here. The resultant data furnish the only available basis for comparing accurately the efficiency of grinding machines. This method is so cumbersome experimentally that it has been little used. As an alternative all sorts of approximations have been proposed. The best of these is complete size analysis by sieving and elutria-tion. Such procedure is very lengthy and difficult to carry out accurately. Furthermore, any sizing method becomes very inaccurate for determining surface with very fine sizes where the ratio of surface to volume becomes very large. To avoid the lengthy and difficult technique of elutriation it has been proposed to estimate the size distribution below 200 mesh from various probability formulas. Such a procedure is at best an engi-neering approximation; at worst it is a mere guess. Some time ago Dr. V. H. Gottschalk2 found that the coercive forces of magnetite powders were directly proportional to the surface area, regard-less of size distribution. It was at once apparent that this furnished a method for determining grinding efficiency quickly and accurately. The only requirement was a single determination of the relation between the work input of the Gross-Zimmerley drop-weight machine and the coercive force of the resultant crushed magnetite.

Jan 1, 1936