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By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By N. A. D. Parlee, E. M. Sacris

OVER 55 years ago, Sieverts and Hagenacker1 and Donnan and shaw2 made determinations of the solubility of oxygen in liquid silver, over a rather short range of temperatures (973° to 1125°C), using quartz bulbs, mainly at 1 atm. From the results of their investigations, Mizikar, Grace, and parlee3 plotted % O vs 1/T and obtained the following straight-line equation for solubility at 1 atm: log % O = 723.7/T - 1.0949 Recent work on the kinetics of the Ag-O2 system394 indicated there might have been some error due to reaction with the direct heated silica bulbs. Thus it became important to redetermine the solubility with the silver contained in a better refractory such as alumina, and by induction heating where the walls of the container were not so strongly heated. It was also desirable to extend the temperature range. A modified Sieverts apparatus of fairly standard type was used except that a special type of reaction tube was employed, Fig. 1. Dried argon with a guaranteed purity of 99.9 pet, and dried medical-grade oxygen with a guaranteed purity of 99.6 pet containing a little nitrogen, were the gases used. The measuring system consisted essentially of a manometer and a water-jacketed 100-cc gas buret with an open-end vertical tube parallel to the buret. This tube has the same diameter as the buret in order to give the same capillary effect on the mercury. A screw leveling device was used with the buret leveling bulb to help provide accurate pressure readings. A 2-mm ID capillary line connected the buret to the reaction chamber, helping to reduce the dead volume, which was determined with argon. The heating medium was a 2.5-kw output induction furnace. The induction coil was made of a 3/16-in. copper tubing with eight turns and an inside diameter of 4 cm. The reaction bulb was made of a quartz tube 18 cm long and 3 cm in inside diameter, Fig. 1. Inside the quartz tube were two alumina crucibles (Mor-ganite Triangle RR, XN10 and XN5) one inside the other. Below these two was an alumina disk. The disk prevented the corners of the outer crucible from expanding against the quartz tube. The solid sample (99.994 + pet Ag), which had been previously cleaned by air oxidation and repeated removal of scum, was placed inside the inner crucible. An alumina disk with a hole at the center covered the two crucibles. In order to decrease the dead volume, an evacuated quartz "filler" tube was placed on top of the crucible cover. The part of the reaction tube above the spherical joint was made up of Pyrex glass with a flat glass top. It was here that a prism was placed to facilitate the use of an optical pyrometer, previously calibrated at the freezing point of silver. This type of reaction bulb and furnace assembly was specially designed for this work, and used in preference to the relatively new water-

Jan 1, 1965

By Nicholas J. Grant, Italo S. Servi

SPECIAL polishing and etching techniques were developed during an investigation of the high temperature mechanical properties of high purity aluminum (99.995 pct Al).* Electrolytic polishing was done successfully in the following electrolyte: 5 ml perchloric acid (72 pct), and 95 ml glacial acetic acid. No special precautions need be taken during the preparation of the electrolyte since no appreciable heat of mixing is evolved. Although the electrolyte is not an explosive, it is recommended that Jacquet's safety rules' be followed during the polishing operation. A voltage of 25 to 60 v gives a good polish in about 2 min at room temperature after preparation on 3/0 metallographic paper. Most of the grain boundaries are visible under the microscope after polishing. Since the current is controlled essentially by the resistance of the bath, it is necessary to keep the anode-to-cathode distance as constant as possible. Accordingly, polishing of irregularly shaped pieces will be difficult. A cooling bath and a stirring system are advisable in order to keep the temperature of the bath uniform and constant. Coarse-grained samples can be macroetched in a few seconds by lowering the voltage below 10 v. This is done after electrolytic polishing, without removing the sample from the bath, Fig. 1. The specimen can be repolished in less than 1 min by raising the voltage above 25 v. The "galvanic etching" technique, which has been described elsewhere,' was found to be helpful not only for macroetching, but also for microetching coarse-grained specimens. In fact, the different orientations of adjacent grains provide good contrast at the grain boundaries, when the sample is observed under polarized light. If the specimen is only partially etched, Fig. 2a, the grain boundaries can be located without completely destroying the appearance of the surface of the specimen. The unetched surface appears black under polarized light. Excellent color contrast is obtained by using a "sensitive tint" plate in the optical system of the microscope. In this case, the unetched surface has a magenta color, while the etched part of the sample assumes different colors varying from green to brown, according to the orientation of the grains. Etch pits were produced on high purity aluminum by using the technique suggested by Lacombe and Beaujard." Good results also were obtained by substituting 70 pct nitric acid for the fuming nitric acid recommended. This gave an etching reagent of the following composition: 70 ml nitric acid (70 pct), 50 ml hydrochloric acid (37.5 pct), and 3 ml hydrofluoric acid (48 pct). An example of the results is shown in Fig- 2b. The outline of the etch pits is revealed sharply if the specimen is observed under polarized light, as shown in Fig. 2c. These metallographic techniques are not suitable for the examination of commercially pure (2s) aluminum. References 'P. A. Jacquet: Metal Finishing (Nov. 1949) 47, p. 62. 21. S. Servi: Metal Progress (1950) 58, p. 732. 3 P. Lacombe and L. Beaujard: Journal Inst. of Metals (1947) 74, p. 1._________________________

Jan 1, 1952

By J. D. Forrester

Many have been prone to credit the decline of professional interest in some branches of mineral industry education to the industrialists and other agencies who use our graduates. We hear the cry that industrial salaries are too low, opportunities for advancement do not exist, and the mineral industry specifically and generally is not interested in the engineer's efforts. Perhaps the time now has come when we should "dress-ranks," examine our practices, and publicize and encourage advanced technical training instead of laying all our troubles elsewhere. There can be no doubt but that industry is interested and stands ready and willing to co-operate. This is demonstrated by the numerous grants-in-aid and co-operative industrial projects which have been made available to those relatively few schools which have been encouraging graduate study and research. There is no dearth of research problems in any of the mineral industry fields and the sooner we realize the great opportunities for constructive, technical research in all areas of our profession the sooner we will reap the benefits of our engineering enterprises by closer liaison and broader understanding with industry. An analysis is offered here of the status of graduate work and research in various phases of mineral industry education in the United States. It is

Jan 1, 1949

By H. R. Peterson, G. J. Lipovetz, W. F. McDermott

One of the major improvements in ore grinding economics in North America has been the introduction of autogenous grinding. Pickands Mather & Co. has been active in the development of autogenous grinding since 1957. This early work led to the application of autogenous grinding to the Wabush mines ore in 1965, with the installation of six 24 ft diam by 8 ft long, 1750-hp mills. Development work recently completed in 1971 on another ore has led to the decision to install five 36 x 15-ft, 12,000-hp mills when this project goes ahead. Between these two decisions lies a tremendous amount of research, development and application of autogenous grinding to a variety of ores. The Pickands Mather Metallurgical and Research Laboratory in Hibbing, Minn., has tested ores from 9 different deposits in its pi- lot plant facility. Some of these deposits have as much difference within their own ore types as there is between the various deposits. Therefore, it is safe to say that over twenty different ore types have been tested and flowsheets developed for commercial applications. Of the nine projects, three are in operation. These are Wabush mines in Labrador, Canada,' Savage River mines in Tasmania,' and The Griffith mine in Red Lake, Ont., Canada.'

Jan 11, 1972

By Edgar T. Wherry

EDGAR .T. WHERRY,* Washington, D. C. (communication to the Secretary ?).-Dr. Pogue's presentation of the facts concerning the emerald deposits is very clear and convincing, and the only addition that I can suggest is a summary of previous theories of origin. He makes it evident that the pegmatite theory is the only one capable of explaining the existing relations, but upon certain details there may be some difference of opinion. If I understand the term pneumatolytic, it does not imply that all the elements concerned in a given deposit were transported as gases, but rather that the crystallization of these elements into the various minerals was favored by the presence of certain gaseous substances, notably H20, C02 and HF. It is highly improbable that the oxides of glucinum, aluminum, chromium, and silicon, which enter into the composition of the mineral emerald could have been transported in the gaseous form. The same is true of the metallic constituents of the parisite and other associated minerals. The explanation suggested, that solutions separated into liquid and gaseous portions, the latter ascending and forming the emerald in the upper portions of the rock only, therefore, seems to me untenable. When two formations exist side by side and one, A, is mineralized while the other, B, is barren, the possible explanations may he classed as (1) chemical, and (2) physical. 1. Some chemical feature of A not found in B might have caused crystallization of certain minerals in the former, which did not appear in the latter. In the present instance both rocks appear to be so similar chemically that no such effect can be looked for. Pogue mentions carbon as a possible precipitating agent, but describes both formations as carbonaceous, so that the difference in the minerals of the two can not be thus explained.

Jan 10, 1916

By E. C. Nelson

An equation is derived for calculating approximately the solubility of nitrogen in an alloy steel over a temperature range from 1200" to 1900°C using data on the effects of alloys on the activity coefficient of nitrogen in iron at 1600°C. Calculated values are compared with experimental data. STUDIES involving the solubility of nitrogen in complex iron alloys have been aided by a system devised by Lanenberg for calculating the solubility of nitrogen in ternary and higher alloys of iron at 1600C using available data on the activity coefficient of nitrogen in binary alloys. Calculated nitrogen solubilities agree well with experimental determinations on complex alloys,' and the calculation procedure is useful when experimental data on specific alloys are not required. A method for extending calculations of nitrogen solubilities in alloy steels to temperatures other than 1600°C would be useful because of the paucity of experimental data in this area. Assumptions which must be made to permit this calculation introduce an element of approximation; however, the calculation is useful in cases where a large number of alloys and temperatures are under consideration, and the precision of experimental measurements is not required. The activity coefficient can be freed from the isothermal restriction of Langenberg's calculation if it is assumed that the solution is "regular". This is a reasonably good assumption for solutions of nitrogen in iron alloys, because usually they are dilute and the heat of solution is relatively small. The presence of large amounts of certain alloying elements would make this assumption less tenable.3 One of the properties of a regular solution is: when "f" is the activity coefficient of a solute and "T" is the temperature in OK. If the activity coefficients at temperatures T and T2 are denoted by subscripts 1 and 2 respectively: The activity coefficient of nitrogen in a complex alloy then can be calculated at any temperature from the sum of the effects of the other solutes on the activity coefficient of nitrogen at 1600°C. It will be convenient to incorporate this expression into an equation which will give directly the logarithm of the solubility of nitrogen at any temperature in the presence of alloys. Two constants, the solubility of nitrogen in pure iron at 1600 "C and the partial molar heat of solution of nitrogen in iron are required. The heat of solution value of 1400 cal at 1600 °C quoted by Kubaschewski and vans will be used. The accuracy of the calculation will suffer if the heat of solution should change materially with temperature. In the absence of experimental data on the temperature dependence of this quantity, it will be expedient to restrict the application of the calcula-

Jan 1, 1963

By C. K. McArthur

THE subject of classification is so broad that this discussion is confined to what the author believes is of prime importance in connection with proper grinding and classification. The years passed have witnessed many noteworthy changes in fine grinding and classification, which have been accompanied by a readjustment of ore-dressing flowsheets for the preparation of better ground and/or sized products at an expenditure of less power, steel and maintenance than formerly. Nowhere in the industry is more being done in the way of experimental work to lower costs than in grinding circuits, because, at best, grinding costs are high. Recent years have indicated that, on the average, finer grinding has a real application. Without careful preparation of the process feed, no operation can be highly efficient or successful. In an earlier paper, the findings of an extensive survey at representative concentrators were presented1. Also, in the year of 1935, a technical discussion was given by Dr. J. V. N. Dorr (Some Notes on Classification Trends in America) before the Chemical, Metallurgical and Mining Society of South Africa In both papers mentioned, much has been said regarding flowsheets, grinding and classification. The author is very familiar with these papers, having had considerable to do with the actual operation of the flowsheets, as well as large mills and classifiers in the work described. Some data from the second paper have been included in the following discussion. Circulating Load In this particular paper it seems advisable to deal with the classification phases of the work that to a major extent govern the success of any closed-circuit grinding unit. The question has often been asked in connection with a closed circuit: "What circulating-load ratio should be carried?" This is really an

Jan 1, 1937

By William P. Blake

In another paper I have described in general the close association of zinc-blende and iron pyrites in the ore-deposits of southwest Wis consin. These two minerals generally occur together at the same horizon, a sheet of one being overlain by a sheet of the other; and also the pyrites is disseminated through the blende to such a degree that the latter is rendered comparatively worthless for the produc tion of spelter. Ordinarily the pyrites, which is mostly the trimetric marcasite variety, occurs in about equal quantity with the blende and is separated by hand-culliug and chipping; but there are large de posits where the ores are so closely mixed that they can neither be separated by culling nor by any mechanical method. The specific gravity of the two minerals is so nearly the same that attempts often made to effect even a partial separation by jigging have proved un. successful. The smelters of zinc-ores in the Mississippi valley will not take ores which carry more than 7 per cent. of iron; and it is therefore necessary to cull the massive ('jack" with great care and at consid erable expense, in order to bring it up to the market-standard of purity. The results of trials to effect a separation of blende and pyrites in other regions have been equally unsatisfactory. The literature of this branch of metallurgy abounds in examples. In Wisconsin efforts have been made in the past to " burn " the mixed ores in heaps, in order to soften or destroy the pyrites, and facilitate its separation from the massive blende. The same method has also been resorted to when galenite is mixed through the substance of the blende, for the purpose of disintegrating the ore, so that it could be separated by jigging. The custom was to pile the ore and the fuel together. As might have been expected, the results were far from satisfactory. As is usual in heap-roast ing, some portions of the ore were overheated and decomposed; zinc was lost by volatilization; the galenite in some portions was

Jan 1, 1894

By W. R. Ingalls

THE present administration has made sincere and effective efforts to reduce the expense of the Federal Government, but it has reached a point beyond which it seems impossible, or anyway extraordi-narily difficult, to go. This is ascribable to the large part of the budget that is represented as war expense. There is no doubt that this spells high taxation for many years to come. Nevertheless, although a large part of the taxation will be attributable to the war, the paying out of the proceeds of that taxation by the government will not be war expense, except in minor part, as will be hereinafter made clear. It will be useful to explain the economic meaning of this situation, for it has bear-ings upon several open questions, such as a bonus to the ex-soldiers, the foreign debt accounts, etc. The expense of the war on the part of the American people was in the main paid concurrently with its prose-cution. This was necessary. Warfare is not conducted with money, but with materials and labor. Except for such previous production as was represented by stocks of goods, the requirements had to be supplied by coincident production. With the end of 1918 our war expense ceased, save for such production, e.g., of ships, that was allowed to run on unchecked, and the indemnities that had to be paid for cancelled contracts. When those matters have been settled we shall be done, barring one important thing. Of course, our war expense began to contract right after the armistice and shrunk rapidly with the demobilization of the troops in 1919. If we had not been able to obtain all needful material from our own sources and had been constrained to borrow it from foreign countries, incurring a foreign debt, we should have been in the quite different posi-tion of having to repay that material, or its equivalent, during subsequent years. The European countries had to come to us for such supplies. This outlines the fundamental difference between their present situations and ours. We were therefore compelled not only to furnish materials and man-power for our own warfare but also much for the Allies.

Jan 3, 1923

By Walter W. Bradley

Mining by hydraulic process of the important gold-bearing gravels of the Sacramento Valley in the basins of the Yuba, Bear and American rivers began in 1853, and continued at an ever-increasing rate for 30 years. In its most active days it reached an annual production of $15,000,000, and averaged $10,000,000 per year over the 30 years. During that period no provisions were made to prevent the debris from being discharged into the water courses, and ultimately large quantities of silt, sand and gravel were washed down to the lower valleys; filling channels, causing overflow of agricultural lands and difficulty in maintaining navigable depths in the Sacramento River. Agitation and suits filed because of these damages finally resulted in the injunction decision of Judge L. B. Sawyer,' in the U.S. Circuit Court, Jan. 23, 1884, which closed down practically all hydraulic mining operations not having means to restrain their debris. In 1893 (approved March 1, 1893), Congress passed the act introduced by Representative Anthony Caminetti, of California, creating the California Debris Commission, composed of three officers assigned from the Engineer Corps of the U.S. Army, and since that time it has been legal and possible within the drainage systems of Sacramento and San Joaquin rivers to conduct hydraulic mining of gold-bearing gravels behind dams built under this commission's permit and supervision. In the watersheds of the Trinity and Klamath rivers, which flow directly to the Pacific Ocean and do not affect navigation or agriculture, operating permits from the California Debris Commission are not required. There is a measure of restriction there, however, through what is known as the Trinity and Klamath River Fish and Game District. Chap. 215, Stat. 1931, in order to secure relatively clear water for the fishing season, provides that between July 15 and October 15 each year there must not be discharged into these rivers debris that will cause a turbidity greater than a content of 50 parts per million in the

Jan 1, 1937

By L. S. Castleman, L. L. Seigle

THE formation and growth of intermetallic phase layers is of considerable practical importance to metallurgists interested in diffusion bonding and cementation processes and has been the subject of extensive qualitative investigation. In contrast, it is somewhat surprising that so little quantitative data have been amassed. The need for additional fundamental work was pointed out by Mehl in 1936,' and persists to a large extent to the present day. The early studies have been reviewed by Rhines,2 and his conclusions have been summarized by Lustman and Mehl3 substantially as follows: 1) All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two metals; however, in some cases, certain of the phases may be too thin to be observed and identified easily. 2) The isothermal growth of intermetallic phases generally obeys a simple parabolic equation of the form X2 = Kt, where x is the thickness of the alloy layer, K the temperature dependent reaction rate constant, and t the time. 3) The rate of thickening varies with temperature according to the Arrhenius equation k = Ae -Q/RT , where k is the parabolic rate constant, A, a temperature independent constant, Q the heat of activation for the process, R the gas constant, and T the absolute temperature. Subsequently, Lustman and Mehl made a quantitative study of the laws of growth in intermediate layers in a number of binary systems, in which one of the components was either zinc or cadmium, and the other component was one of the following: nickel, copper, silver, cobalt, gold, iron, or Monel metal; the interdiffusion times used were for the most part less than 24 hr. It was found that the simple parabolic law was not obeyed in general, but that a generalized parabolic law of the form xn = kt was valid, where n was a temperature dependent constant; also,

Jan 1, 1959

By G. U. Greene

The various lead producers have given the subject of lead drosses much attention in recent years but the problem of their economical treatment is yet to be solved. Formerly the copper in the furnace feed was removed from the furnace in the form of matte. The speiss at that time consisted principally of the iron arsenide. The practice today is to roast off most of the sulphur and the copper in the feed forms a dross in the furnace, which is removed from the furnace with the lead. This material is poured into the drossing kettles and allowed to cool down to but slightly above the freezing point of lead. The copper dross, containing almost all of the arsenic and part of the antimony, is skimmed off and treated in a small reverberatory furnace at most plants. This is essentially a liquation process. The skimmed dross contains from 70 to 80 per cent lead, and much of this lead is liquated out. The products from this treatment are: (1) impure lead, (2) speiss and (3) matte. The speiss from the reverberatory furnace was studied in this research. The literature on the subject is of very little assistance, as almost no work has been done on the problem of establishing the exact identity of the various phases present. One author(1)† states that speiss consists of a series of isomorphous compounds of the general formula FexAsy in which the Fe may be replaced by Ni, Co, Cu, Pb, Ag, Au, Pt, Zn, Cd and the As replaced by Sb, S and Bi. Hofman(2) states that the iron arsenide present is Fe5As. Experimental Work In the present research, the author used for methods in an attempt to determine the composition of the various phases: (1) chemical, (2) microscopic, (3) roentgenographic and (4) thermal. Previous to this research, considerable time had been spent making analyses of different speisses, but unfortunately no very definite conclusions could be made as a result of these analyses.

Jan 1, 1937

By Zay Jeffries

THIS paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.1 The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the Ar transformations. 4. The grain-size refining of steel and iron is brought about by the combined. effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation .products do not inherit their grain size from the austenite on cooling through the transformation range for does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite ,grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. 1n this instance small austenite grains may form very large ferrite grains on cooling through Ar3.

Jan 11, 1917

By O. George Specht, Carl A. Zapffe

IN recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experimentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. GROUP I: REDUCTION WITH HYDROGEN Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1946

By J. L. Rodda

THE desirability of a uniformly sized abrasive for metallographic polishing has probably been recognized in a general way for a long time. Certainly all metallographers have recognized the damage that can be done to a polished surface by a piece of grit, especially if one of the softer metals, such as zinc or aluminum, is being polished. It is to be doubted, however, whether many metallographers have had any adequate idea of the particle size of the abrasives they were using or of the range of sizes encountered in any given grade of abrasive. At any rate, the descriptions of abrasives for metallographic work found in the literature are generally very meager. It was with the idea of securing an abrasive with a limited range of particle size that a study of this problem was commenced. Commercial abrasives, even when recommended for metallographic work, are made up of particles of varying sizes. One such abrasive contains some particles so fine that they remain in suspension for days and other particles so coarse that they settle at the rate of 3 in. per minute. It is evident that the coarsest particles are over 100 times the diameter of the smallest ones, or over 1,000,000 times the volume. The hopelessness of avoiding scratches under these conditions is evident. Vanderwilt1 has described a laboratory method for grading abrasives in which the elutriator is used. Le Chatelier's method, described by Goerens,2 also makes use of an elutriator. However, the elutriator is too slow for this purpose and requires too delicate a control for the range of sizes desired. The method of stirring up the abrasive in water, allowing it to settle for as given time, then drawing a measured depth off the top of the suspension, has been finally adopted as the simplest proce-dure. The largest particle in a given portion is. then determined by Stokes' law:3

Jan 1, 1931

By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The role of surface charge in soluble salt flotation, which was developed in Part I, is extended to relate the theory to the specific phenomena of KCI-NaC1 separations. Temperature-collector solubility relationships, metal ion activation, and particle size effects are discussed. The initial paper in this series developed and presented the hypothesis that one of the mechanisms of soluble salt flotation may involve electrical attraction between the collector and mineral surface. This hypothesis was developed from a combination of experimental data and free energy calculations, and details of the logic are presented in this first paper.* The studies have indicated that KC1 has a positive surface charge and NaCl a negative charge. KC1 can therefore be floated with sulfonate ion (RSO;) or with an aqueous polar species such as the aqueous amine chloride, RNH3C1(,,). The chloride end of the RNH3C1(,,) molecular dipole is probably negative and will be attracted to the positive surface of the KC1 particles and absorb (actually probably fit into a vacant chloride site) on the mineral surface. The amine end of the collector molecule would extend into the solution phase and provide the air avid surface required for flotation. NaCl particles are floated by such collectors as aqueous molecules of fatty acid salt, RCOONa(,,), in which the positive inorganic end of the dipole is attracted to the negatively charged surface of the NaCl and, in this case, adsorb and probably fit into a vacant sodium site on the surface. The aminium cation, RNH~, should also be a collector for NaC1. For certain collectors, actual precipitates of the collector must be formed before a sufficient amount of the polar aqueous molecule is present to effect flotation. In a system of this type there is a three-way equilibrium between: Aqeous Molecular Solid Precipitate - A of the Collector (Not Dissociated) . Ionic Species (Dissociated). The controlling equilibrium is probably between the precipitated form of the reagent and the aqueous

Jan 1, 1969

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1'2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947