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By C. H. Samans, G. F. Tisinai, J. K. Stanley

The addition of nitrogen (0.10 to 0.20 pct) to Fe-Cr-Ni alloys of simulated commercial purity results in a real displacement of the u phase boundaries to higher chromium contents. The effect is small for the (Y + s)? boundary, but is pronounced for the (y + a +s)/(y + a) boundary. Although there is an indication of an exceptionally large shift of the n boundaries to higher chromium contents, especially in steels with nitrogen over 0.2 pct, the major portion of this apparent shift results from the fact that carbide and nitride precipitation cause "chromium impoverishment" of the matrices. The effect of combined additions of nitrogen and silicon to the Fe-Cr-Ni phase diagram is demonstrated also. Nitrogen can nullify the effect of about 1 pct Si in shifting the (y + o)/? phase boundary to lower values of chromium at all nickel levels from 8 to 20 pct. NItrogen can nullify this U-forming effect of about 2 pct Si at the 8 pct Ni level, but not at the 20 pct Ni level. The alloys studied were in both the cast and the wrought conditions. There are indications that the u phase forms more slowly in the cast alloys than in the wrought alloys if both are in the completely austenitic state. The presence of 6 ferrite in the cast alloys accelerates the formation of U. Cold working increases the rate of o formation in both cast and wrought alloys. THE major improvement in Fe-Cr-Ni austenitic alloys in recent years has been in the addition or removal of minor alloying elements to facilitate better control of corrosion resistance, sensitization, and heat resistance. One shortcoming of the austenitic Fe-Cr-Ni alloys, which never has been completely circumvented, is their propensity toward u formation. In the AISI-type 310 (25 pct Cr-20 pct Ni) and type 309 (25 pct Cr-12 pct Ni) steels, sufficient amounts of u phase can form, if service or treatment is in a suitable temperature range, to cause severe embrittlement. Also, there is a growing conviction that this phase may be contributory to some unexpected decreases in the corrosion resistance of certain of the 18 pct Cr-8 pct Ni-type steels. The present paper discusses the effect of nitrogen additions on the location of the (r+u)/d and the (y+a+u)/(y+a) phase boundaries in the ternary Fe-Cr-Ni system, for cast and wrought alloys of simulated commercial purity, and in similar alloys containing up to about 2.5 pct Si. The objective is to define compositional limits for alloys which will not be susceptible to u formation when used near 1200°F (650°C). An excellent review of the early studies of the u phase in the Fe-Cr-Ni system has been compiled by Foley.1 Rees, Burns, and Cook2 have determined a high purity phase diagram for the ternary system, whereas Nicholson, Samans, and Shortsleeve3 are- stricted themselves to a portion of the simulated commercial-purity phase diagram. Both groups of investigators show almost an identical position for the commercially significant (y+u)/y phase boundary. Further comparison of the work of the two groups indicates that, below the 8 pct Ni level, the commercial alloys have a decidedly greater propensity toward u formation than the high purity alloys. The two groups of workers agreed that both the AISI-type 310 (25 pct Cr-20 pct Ni) and the type 309 (25 pct Cr-12 pct Ni) steels are well within the (y+~) region and that the 18 pct Cr-8 pct Ni-type alloys straddle the U-forming phase boundaries. Nicholson et al.3 showed, in addition, that these boundaries shift toward lower chromium contents if greater than nominal amounts of silicon or molybdenum are added. The effect of nitrogen on the location of the s phase boundaries in the Fe-Cr-Ni system has not been known with any certainty. In 1942, an approach to this problem was made by Krainer and Leoville-Nowak,' but at that time they apparently were unaware of the slow rate of s formation in strain-free samples and aged their samples for insufficient times, e.g., 100 hr at 650°C (1200°F) and 800°C (1470°F). For this reason, it would be expected that their (y+ u) /y boundary would be shifted toward lower chromium contents (restricted ?-field) when equilibrium conditions were approximated more closely. Procedure for Studying the Alloys The alloys used were prepared in the following way: Heats of 200 lb each were melted in an induction furnace. A 5 lb portion of each heat was poured into a ladle containing an aluminum slug for de-

Jan 1, 1955

By W. Rostoker, A. S. Yamamoto, K. Anderko

ALTHOUGH the corrosion resistance of magnesium and its alloys is closely related to iron content, there has been no direct measurement of the solid solubility of iron in magnesium. Bulian and Fahrenhors;1 and Mitchel]2 agree that pure iron or a limited terminal solid solution crystallizes from the Mg-rich liquid. For this reason a magnetic-moment method was selected to estimate that portion of the total iron content which is not in solid solution. Since iron in solid solution in magnesium cannot contribute to ferromagnetism, the difference between chemical and magnetic-iron analyses should yield the solid solubility. By experimentation it was found that the melting of pure sublimed magnesium (99.995 wt pet purity) in Armco-iron crucibles at about 800°C is a convenient way to introduce small amounts of iron. Melts retained 5, 10 and 20 min at 800°C analyzed 0.003,, 0.005,, and 0.018 & 0.001 weight pet Fe, respectively, after being stirred, heated to 850°C, and cast into graphite molds. The as-cast alloys were pickled in acid (dilute HC1 + HNO3), annealed at 600°C for 3 days, scalped on a lathe to remove the pitted surface, pickled again, extruded at about 100°C to 3-mm wire, reannealed 41/2 days at 500°C, and water-quenched. The specimens were again scalped, pickled, and used both for chemical and for magnetic analysis. Most of the precautions described were intended to prevent iron pickup by contact with tools or superficial iron enrichment by volatilization of magnesium during heat-treatment. It is believed that the specimens ultimately used for test were homogeneous and characteristic of phase equilibria at 500°C. Magnetic Analyses A susceptibility apparatus of the Curie type was used for magnetic analyses. Field strengths of up to 10,400 oersteds could be generated. By this method, an analytical balance measures the force of attraction which a calibrated magnetic field exerts on a suspended specimen. The force equation is as follows f/m = M dh/dy where f/m = force per unit mass of sample M = magnetic moment per unit mass dH/dy = magnetic field gradient The dH/dy characteristic of the instrument is determined by the use of a standard palladium sample, and the calibration is made independently for all values of H. Since a large finite field is required to saturate an assembly of ferromagnets, it is necessary to measure the apparent magnetic moment for increasing steps of H until a saturation value is obtained. The percentage of iron in the sample as free ferromagnetic iron may then be computed simply C= 100 (M1/M1) where C = percent content of undissolved iron in sample M1 = saturation magnetic moment of sample per unit mass M1 = saturation magnetic moment of iron per unit mass taken as 217 emu-cm per gm There is no serious difficulty in applying this method except for the unusual magnetic behavior of very fine particles of ferromagnetic substances. It has been found and is the basis for a widely accepted theory that with sufficient subdivision, the magnetic fields required to saturate and the coercive force after saturation rise to exceedingly high values. Recent work on precipitates of Fe and Co from copper solid solutions8 showed that about 5000 oersteds were necessary to approach saturation. The magnetic moments as a function of field strength measured in the present investigation are listed in Table I. Only the 0.018 wt pet Fe alloy yielded a magnetization curve with a fairly well-defined saturation plateau at 3.76x10 -2 emu-cm/ gm. This corresponds to 0.017 & 0.001 wt pet Fe in the alloy. This indicates that the solid solubility must be of the order of 0.001 wt pet Fe. The magnetic-moment data of the other two alloys are badly scattered, indicating that the amount of ferromagnetic iron in these samples is so low that the magnetic forces acting on them cannot be measured accurately by the analytical balance used. Nevertheless, the fact that even the 0.003, wt pet Fe alloy shows ferromagnetism indicates that the solid solubility must be below that value. Acknowledgment This work was sponsored by the Pitman-Dunn Laboratory of Frankford Arsenal, Philadelphia, Pa. The support and permission to publish are gratefully acknowledged. References W. Bulian and E. Fahrenhorst: Zeic. Metallkunde, 1942, vol. 34, pp. 116-170. 2 D. W. Mitchell: AIME Transactions, 1948, vol. 175, pp. 570-578. 3 G. Bate, D. Schofield, and W. Sucksmith: Philosophical Magnsine, 1955, vol. 46, pp. 621-631.

Jan 1, 1959

By D. J. McAdam

RESULTS of investigation of corrosion-fatigue of metals at the U. S. Naval Engineering Experiment Station, Annapolis, Md., have been discussed by the writer in several recent papers. 1.2.3.1 In those papers references were also given to the work of Haigh in 1917.6 Efforts by the writer to obtain a better understanding of some of the factors involved in corrosion-fatigue finally developed into a general investigation of the effect of time and cyclic stress on corrosion of metals. Corrosion fatigue of Metals As described in the papers mentioned, rotating-cantilever specimens, conically tapered so that the stress is nearly uniform over a length of about 1.5 in., were subjected to simultaneous fatigue and corrosion. For this purpose a stream of water was diagonally applied so as to sweep the specimen from the outer to the inner fillet and surround the stressed surface with water. The fresh water is a calcium carbonate water, the composition of which has been given in a previous paper .2 The salt water is Severn River water having a saline content about one-third that of sea water. The previous papers described results obtained with ferrous and nonferrous metals. The experiments showed that even slight corrosion simultaneous with fatigue may cause failure at nominal stresses far

Jan 1, 1928

By George J. Bancroft

INTRODUCTION. IT is unnecessary to repeat here the contents of many valuable contributions to this subject which have appeared in the Transactions and in the publications of the U. S. Geological Survey. As a basis for the further suggestions of this paper, the following are the most important: 1. The investigation of J. R. Don,1 showing the gold of certain Australasian veins to have been deposited by ascending solutions, and not by lateral secretion. 2. The theory of Prof. Posepny,2 distinguishing the vadose from the deep circulation, and ascribing the origin of certain classes of ore-deposits to ascending solutions of the latter class. 3. The theory of Prof. Van Hise,3 as to the underground circulation and the primary enrichment of veins thereby. 4. The paper of Prof. J. F. Kemp,4 showing that ore-deposits are largely the products of " expiring vulcanism." Many of Prof. Kemp's, ideas have been widely adopted by mining men. 5. The theory of secondary enrichment, so lucidly expounded by Mr. S. F. Emmons.5 This theory, dealing with, the rearrangement of ore-bodies after primary mineralization, has been generally adopted, and seems to me to have been as completely proved as the nature of the case permits. There are two facts which I think should be constantly borne in mind in formulating a theory of the genesis of ore-

Jan 1, 1913

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

The object of this paper is to describe the adaptation of electrical resistivity measurements to the particular case of exploration in which the surface is an expanse of water (river, lake, sea). Water in itself does not constitute an obstacle to electrical exploration. It is merely an overburden, which is fluid instead of being solid, and as a consequence the routine of the measurements has to be modified. Also, in many instances, the liquid under consideration is highly conductive (salt water). This introduces an additional difficulty into exploration work, and has to be overcome by the geophysicist. We do not propose to discuss here the basic principles of electrical resistivity measurements, which have been dealt with in various previous papers,' but will simply recall the two fundamental techniques which govern its field application: 1. Horizontal exploration, or method of the resistivity map, in which a series of electrical measurements are carried out at various stations, keeping the same electrode spacing. Thus, a horizontal layer of the subsoil, of a practically constant thickness, is explored. 2. Vertical exploration, or "vertical sounding"2 method, in which a seriesr of measurements is made with increasing electrode spacings at one or several stations. In this way, the apparent resistivity is determined at a given station for various increasing thicknesses of the ground.

Jan 1, 1934

By P. Somasundaran, K. P. Ananthapadmanabhan

A knowledge of the role of effects and interactions of chemical species is important in developing an understanding of the behavior of mixed minerals and natural ores in beneficiation processes such as flotation and flocculation. In this study the role of such species was examined for the calcite-apatite system by conducting flotation of each mineral in various supernatants prepared by mixing with water. Supernatants of apatite and even that of calcite depressed the flotation of calcite markedly in the pH range of 5 to 13. Addition of Ca(NO3)2, K2C03, and K3P04 also produced definite effects under various pH conditions. Apatite flotation was also affected by the mineral supernatants and by carbonate and phosphate solutions. The results are analyzed in terms of the surfactant's solubility properties and the mineral's electrochemical and dissolution properties. While depression of calcite flotation by the dissolved species is found to be governed by depletion of oleate by bulk precipitation, the depression of apatite flotation is caused by the carbonate and phosphate species in the system. Turbidity measurements and a thermodynamic analysis of possible interactions in the system support these considerations. The effect of the supernatant of minerals on their own flotation suggests the important role of kinetics of various surface interactions in comparison to that of mineral dissolution.

Jan 1, 1985

By Jack Parker

The White Pine mine site lies five miles south of Lake Superior in Ontonagon County, Mich. Copper sulfide, mixed with some native copper, is mined by a room-and-pillar system from gently dipping Upper Kewee-nawan sediments. Depth of mining now varies from 700 to 1800 ft and the ore body continues to a depth of at least 3400 ft. An area roughly 21/2 miles square has already been mined. Mining height has varied from 61/2 to 22 ft. A rock mechanics program was set up in late 1963 to promote safety and mining efficiency. This note reports some of the findings. Rock Strength Compressive strength of small, dry specimens of sandstones, siltstones, and shales from the ore zone varies from 20,000 to 30,000 psi. This is intermediate between the softer coal mine sediments and the meta-morphic and igneous rocks of hard rock mines. Annual Cycle of Rock Failure Since 1963, every roof and pillar failure involving more than a few tons of rock has been examined and documented. Some 1500 stations have been installed for measuring convergence, -c1/1000 in., with Invar extensometers. At first it was thought that there was some kind of a cycle of roof failures; perhaps annual, perhaps even elated to the moon or to earth tides, but records (see

Jan 1, 1971

By A. W. Fahrenwald

THE absolute efficiency of crushing and grinding in a ball mill is not known. A number of investigators have made calculations to this end and have presented efficiency figures. Two factors have prompted further investigation of this subject: (1) the unbelievably low magnitude of the values offered, and (2) a desire to obtain, if possible, true relationships between the relative efficiencies of a ball mill operating under varying conditions. A useful forward step in the study of mill efficiency was made when Martin1 and Gross and Zimmerley2 proved the correctness of Rittinger's law, and incidentally the incorrectness of the so-called Kick law, and when Gross and Zimmerley3 determined and gave surface values for Tyler sieve-sized quartz. These data are probably accurate throughout the range of the sieve scale, but on -400 mesh (which is the finest sieve available), the surface data, as obtained by the hydrofluoric acid disso-lution method, are of doubtful reliability. Any inaccuracy existing in surface determinations of -400-mesh material, especially when comparing runs in which varying quantities of this product are formed, will cause the resulting relative mill efficiency values to be distorted. Moreover, knowing surface accurately, the efficiency calculations require a surface energy figure. Two such figures are to be found in literature, one by Edser4 and one by Martin.5 Edser's surface energy

Jan 1, 1931

By M. J. Duggin

Evidence is produced below to show that the carbide "Mn,C," reported by Kw,and ersson' is really a mixture of two carbides. One is an Fe-Mn carbide which is probably isomorphous with hexagonal Mn15C4, reported by Bouchand and Pruchart.' The othev is a tetragonul Fe-Mn carbide with cell dzmensions close to those reported previously by the author3 for an Fe0.1Mno. carbide. IN a recent investigation several Fe-Mn carbide specimens, each weighing about 5 g, were prepared in a manner previously reported.3 Debye-Scherrer X-ray photographs were taken of at least two samples from different parts of each specimen using a 114.6-mm-diam camera. The exposure time was 2 hr using filtered chromium radiation, a tube voltage of 35 kv and a tube current of 10 ma. In the case of one specimen, which contained nominal weight percentages of iron, manganese, and carbon of 9.40, 84. 6,, and 6.0, respectively, duplicate chemical analyses indicated f1.2 and 5.5 wt pct C to be present in the two samples taken of the specimen: no graphitic carbon was detected. One powder-diffraction pattern of this specimen indicated the presence of the tetragons: carbide reported earlier,3 (a = 6.772A, c = 9.427A), plus cementite (O), plus an unknown structure. The second powder-

Jan 1, 1970

By A. M. Gaudin

TEN years ago Taggart, Taylor and Ince1 described a workable, convenient apparatus for the measurement of contact angles be-tween cleaved, ground or polished particles and captive bubbles. Wark and Cox2 and Wark and Sutherland3 have done an im-mense amount of experimental work with this apparatus. Their work has had as principal object the determination of "con-tact curves." Contact curves are Cartesian charts in which pH (or some other variable) is plot-ted against quantity of modifying agent. The rectangular area is broken into two or more curvilinear areas separated by the contact curve. The curve indicates that a sharp demarcation exists between condi-tions that bring about sticking of particles to bubbles and conditions that do not pro-duce sticking, The type curve appears in the TRANSACTIONS as Fig. 1, page 248, volume 112. Wark and Cox offer data to show that the contact angle has a value determined by and characteristic of the agent used. Wark and Cox also make the statement that they believe this value is independent of concen-tration (ref. 2a, p. 209), They say: It is suspected that, given sufficient time and provided that there are no disturbing factors. the full ethyl xanthate angle (corresponding to a complete xanthate film) would be obtained in every case where contact occurs.

Jan 1, 1940

By C. L. Dake

Chemistry of Iron Solution IRON is much more soluble in the ferrous than in the ferric form. Where, as in the case of the ferrous silicates and the sulphides, the iron is already in the ferrous form, it may go at once into solution and be removed, upon the breaking down of the parent rock. If in the ferric form, it must first be reduced; usually by the decay of organic matter, the demand of the decaying carbonaceous matter for oxygen being so great that the latter is abstracted from the ferric compounds and the iron is thereby reduced and rendered' soluble. The iron may go into solution as the sulphate, or in the presence of excess CO2 as ferrous carbonate. It is probably soluble as salts of the organic acids.1 Recent work indicates that these are important in the formation of bog ores.2 There is considerable variety of opinion concerning the behavior of these organic compounds.3 The secretions about the roots of plants and trees also cause the solution and removal of iron and a consequent bleaching of the soil.4 While the matter is not yet well understood, we can probably say definitely that the so-called organic acids are a group of colloids which possess slightly acid properties, and the salts of which are partly soluble

Jan 7, 1915

By Nicholas Kowall, K. L. Clark

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By K. L. Clark, Nicholas Kowall

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By W. L. Mamme, G. Y. Chin

The problem of selection of the active slip systems for a crystal undergoing an arbitrary strain was analyzed by Taylor and by Bishop and Hill in terms of a minimum (internal) and a maximum (external) work criterion, respectively. These two criteria have now been generalized to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (noncrystallographic) pencil glide. The generalized treatment also takes into account the possibility of a Bauschinger effect and of unequal hardening among the shear systems, which were considered in the Bishop and Hill work. Optimization techniques of linear and nonlinear programming are shown to be applicable for the numerical calculation of the minimum or maximum work. In the case of crystallographic shear, the constraint functions are linear and hence the optimal work is obtained as the saddle value of the lagrangian function Wi(y) e minimum and W,(u) + (a) for the maximum, where Wi is the (internal) work, We is the (external) work, Y is the crystallographic shear strain, u is the applied stress, and and are constraints. It is shown that the Lagrangians are functionally the same and the saddle value of one problem is identical to the saddle value of the other, proving that the two analyses are completely equivalent. In the case of pencil glide, although the constraint functions are nonlinear and neither convex nor concave, the equivalence of the optimal values to the saddle value of the Lagrangian (which is again identical for both problems) is still valid. WHEN a crystal deforms plastically by crystallographic shear, five independent shears are generally required to accommodate five independent strain components specifying the deformation. Assuming slip as the only shear mechanism, Taylor1 in 1938 analyzed the deformation in terms of a minimum work criterion. He hypothesized that of all combinations of five slip systems which are capable of accommodating the deformation, the active combination is that one for which the internal work C is a minimum, where 1 TI is the critical resolved shear stress for slip on the 1-th slip system and is the corresponding simple shear. By further assuming equal 72 for all equivalent slip systems and no Bauschinger effect, Taylor re- duced the minimum work problem to one of minimum and applied the analysis to the case of axisym- Metric flow by {111}(110) slip in fcc crystals. However, he did not consider the question of whether the resolved shear stress has in fact attained the critical value for slip on the newly found active systems without exceeding it on the inactive systems. In 1951 Bishop and ill' put forth the maximum work analysis in which slip is again assumed as the only deformation mechanism. In this analysis, the work o1 done in a given strain ij by a stress ujj not violating the yield condition is maximized. In addition, the analysis takes into account the possibility that the critical resolved shear stress for slip may not be equal among the slip systems and that the slip behavior may exhibit the Bauschinger effect. As with Taylor, a single set of slip systems—{111)(110) — was analyzed numerically. It thus appears that the Bishop and Hill treatment is on a more sound physical basis than the Taylor treatment. However, Bishop and Hill showed that where there is equal hardening among all slip systems and when there is no Bauschinger effect, Eq. [11 ] of Ref. 2, as assumed by Taylor, the results of their maximum work analysis are the same as those of Taylor's minimum work analysis. Hence at least under those conditions there is an implication that the Taylor analysis does lead to a critical resolved shear stress for slip on the predicted active systems without violating the yield condition on the inactive systems. Recently, the Taylor analysis was applied for numerical solutions of the axisymmetric flow problem, for slip on {110}(111), {112}(111). {123)(111) systems as well as a mixture of all three sets of svstems."1 Computational techniques based on the optimization theories of linear and nonlinear programming4 were employed in these solutions. The same techniques were employed in the solutions of an axisymmetric flow problem of deformation by slip on (111) (110) systems and twinning on (111)(112) systems5 which had been considered theoretically from a modified Taylor approach. The utilization of these techniques has led to the realization that the solutions of Taylor's minimum work problem imply the solutions of Bishop and Hill's maximum work problem. The two problems turn out to be dual problems in the well known sense of mathematical programming. It is thus the purpose of this paper to first generalize the minimum and maximum work analyses to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (non-crystallographic) pencil glide, as well as the possibility of a Bauschinger effect and of unequal hardening

Jan 1, 1970

By Robert C. Stephenson

LARGE deposits of titaniferous magnetite occur associated with anorthosite and gabbro in the Lake Sanford area, Essex County, New York. The ore, gabbro, and anorthosite show consanguineous relations. Anorthosite grades through gabbroic anorthosite into gabbro but is locally intruded by gabbro. Structural and petrographic evidence suggests that gabbro was differentiated from anorthosite by filter pressing. Field and laboratory study of ore occurrences indicates that an ore residuum concentrated in the gabbro through magmatic segregation by normal crystallization and flowage. Ore occurs as bands which grade into gabbro, and also as large masses which replace anorthosite. Ore in the gabbro is finer grained and richer in ilmenite than ore in anorthosite.

Jan 1, 1945

By Sylvan Cromer

The need for a clear understanding of the physical nature of the flow of gas-liquid mixtures in vertical pipes is ever becoming more apparent. This type of flow is encountered when gas and oil are produced from a well; when water is removed from gas wells with siphon lines and when liquids are elevated by means of air or gas lift. Although a number of investigator1-7 have published data on the flow of gas-liquid mixtures, in only a few cases has the experimental setup been devised to permit visual study. In the fields of heat transmission, such as the boiling of liquids and the study of the critical phenomena of the hydrocarbons, researchers have been able to throw additional light on heretofore unexplainable happenings through actual observation in glass apparatus. This investigation was therefore undertaken in order to obtain qualitative as well as quantitative results for air-water flow. Experimental Apparatus and Procedure The flow column used in these tests was made of standard 2-in. pipe and was approximately 98 ft. in height. Pyrex observation sections 2 ft. long having the same internal diameter as the wrought-iron pipe were placed at 14-ft. intervals in the column. The bottom of the tube was cut off square and terminated in the mixing chamber. No perforated nipple or footpiece of any kind was used. To the top of the column was fastened a semicircular return bend having a 4-ft. radius. The flow column was supported by a standard cable-tool drilling derrick (Fig. 1) into which were built observation platforms at each Pyrex section.

Jan 1, 1940

By Sylvan Cromer

The need for a clear understanding of the physical nature of the flow of gas-liquid mixtures in vertical pipes is ever becoming more apparent. This type of flow is encountered when gas and oil are produced from a well; when water is removed from gas wells with siphon lines and when liquids are elevated by means of air or gas lift. Although a number of investigator1-7 have published data on the flow of gas-liquid mixtures, in only a few cases has the experimental setup been devised to permit visual study. In the fields of heat transmission, such as the boiling of liquids and the study of the critical phenomena of the hydrocarbons, researchers have been able to throw additional light on heretofore unexplainable happenings through actual observation in glass apparatus. This investigation was therefore undertaken in order to obtain qualitative as well as quantitative results for air-water flow. Experimental Apparatus and Procedure The flow column used in these tests was made of standard 2-in. pipe and was approximately 98 ft. in height. Pyrex observation sections 2 ft. long having the same internal diameter as the wrought-iron pipe were placed at 14-ft. intervals in the column. The bottom of the tube was cut off square and terminated in the mixing chamber. No perforated nipple or footpiece of any kind was used. To the top of the column was fastened a semicircular return bend having a 4-ft. radius. The flow column was supported by a standard cable-tool drilling derrick (Fig. 1) into which were built observation platforms at each Pyrex section.

Jan 1, 1940

By Sylvan Cromer

THE need for a clear understanding of the physical nature of the flow of gas-liquid mixtures in vertical pipes is ever becoming more apparent. This type of flow is encountered when gas and oil are produced from a well; when water is removed from gas wells with siphon lines and when liquids are elevated by means of air or gas lift. Although a number of investi-gators1-7 have published data on the flow of gas-liquid mixtures, in only a few cases has the experimental setup been devised to permit visual study. In the fields of heat transmission, such as the boiling of liquids and the study of the critical phenomena of the hydrocarbons, researchers have been able to throw additional light on heretofore unexplainable happen-ings through actual observation in glass apparatus. This investigation was therefore undertaken in order to obtain qualitative as well as quanti-tative results for air-water flow. EXPERIMENTAL APPARATUS AND PROCEDURE The flow column used in these tests was made of standard 2-in. pipe and was approximately 98 ft. in height. Pyrex observation sections 2 ft. long having the same internal diameter as the wrought-iron pipe were placed at 14-ft. intervals in the column. The bottom of the tube was cut off square and terminated in the mixing chamber. No perforated nipple or footpiece of any kind was used. To the top of the column was fastened a semicircular return bend having a 4-ft. radius. The flow column was supported by a standard cable-tool drilling derrick (Fig. 1) into which were built observation platforms at each Pyrex section.

Jan 1, 1939