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By AIME AIME

TUESDAY afternoon the annual meeting was devoted to a general session, in the auditorium, on production control. George Otis Smith presided and in opening the meeting recalled that the session in 1920 on the stabilization of the coal industry was the first time this subject had been discussed by Institute members in a general session and then introduced Carl Snyder, of the Federal Reserve Bank of New York, who spoke on "Long-time Growth and the Factors In Its Variations." He spoke without notes and a full presentation of his views must be deferred until the stenographer's report is available. He said that of the total production some 80 to 90 per cent represents goods for consumption and the other 20 to 10 per cent for construction. He discussed various indices of production, concluding that bank clearings are the best, and showed by charts that when they are plotted, allowing for various disturbing factors, they are seen to increase quite regularly at the rate of about 4 per cent per year. The production curve rises at only 3y2 per cent per year, because agricultural production does not in- crease as fast as manufacturing postal revenues in- crease at the rate of 5 per cent per year while the use of electricity increases twice as fast.

Jan 1, 1929

By R. S. Sherwin

The extractive metallurgy of primary aluminum from its ores is discussed with special attention to the production of alumina from high grade ores by the Bayer process, including differences between American and European practice and a brief description of some processes for lower grade ores and the electrolytic reduction of the oxide to aluminum. METALLIC aluminum is not found in nature, but the oxides, hydroxides, and especially the silicates are plentiful. The estimated percentage of in in the crust of the earth is about 8 pct while that of iron is about 5 pct. By far the larger portion of this is combined with silica in the form of various clay minerals and igneous silicate rocks. From the point of view of extractive metallurgy of aluminum, these are low grade ores while the better qualities of bauxite are the high grade ores. There have been various definitions of bauxite but perhaps the best definition at the present time is that bauxite is a rock or earth commonly used as an ore of aluminum or its salts in which the aluminum is present predominantly as a hydrate or a mixture of hydrates and hydrous oxides. It contains varying amounts of oxides of silicon, iron, and titanium and traces of compounds of some of the less common elements. The silica is mainly combined with alumina as clay or clay minerals which are hydrous aluminum silicates, although a part of it may be present as quartz sand. On the American continents, the alumina is mainly present as gibbsite, Al2O3 . 3H2O, and the same may be said of the best known deposits of the Dutch East Indies and some of the deposits in India. In France and other countries in Europe as well as in Africa, the alumina is present mainly as boeh-mite, A12O3 . H2O, but in some of these deposits it is mixed with minor amounts of gibbsite. Some other deposits, such as those in the islands of Haiti and Jamaica, evidently contain two or more hydrates or hydrous oxides of alumina in varying proportions. Perhaps the main portion of the alumina may be present as gibbsite and boehmite with the proportion between the two varying rather widely. In the silicate minerals, including clay, the alumina is chemically combined with silica and has not been separated satisfactorily by mechanical or physical ore-dressing methods. Low grade bauxites are mixtures of hydrates, usually gibbsite or boehmite, with clay, iron oxides, etc. In some low grade bauxites, it is possible to separate a portion of the gibbsite or boehmite, which may be present as relatively hard and coarse particles, from soft or finely divided clay minerals by log washing or similar methods. This has been applied to the product of some mines or parts of them, but on other ores it is not applicable. In some cases the gibbsite or boehmite is almost as fine and soft and of nearly the same specific gravity as the clay minerals so that washing and gravity separations are not successful. The iron oxide, the clay minerals, and a part of the titanium minerals are often so finely dispersed in the ore that any of the physical mineral separation methods, including separations by gravity, particle size, flotation, and electrostatic or magnetic separation, have not been commercially SUCCESSFUL except on relatively small lots of ore. For these reasons, the only available methods of separation on the general run of ores have been methods which would be classed as chemical rather than physical or mechanical separations. Aluminum oxide can be reduced by carbon at temperatures above 1800°C to form metallic aluminum and aluminum carbide or nitride. The temperature for rapid reduction of aluminum oxide to metallic aluminum is about the boiling point of aluminum and above the temperatures necessary to reduce iron, silicon, and titanium so that the direct reduction of an aluminum ore with carbon will produce an alloy of aluminum, iron, titanium, silicon, etc., which may be mixed with carbides and nitrides. Also a large amount of the reduced aluminum may be lost as a vapor except in the presence of some alloying agent such as copper or other metals. While it is possible to refine such alloys or mixtures so as to produce commercially pure aluminum, the methods which have been found are too expensive for the present market. One direct reduction method which found limited commercial use in Germany during World War II was the direct reduction of a mixture of clay containing very little

Jan 1, 1951

Mr. A. Bement, Chicago, Ill. (communication to the Secretary*) :—Mr. Campbell, in proposing his method of sampling coal-seams, has rendered an important service in insisting on the presentation of an adequate history of the sample; and it is to be hoped that his suggestion will meet with further recommendation. In my opinion it is fully as important that a complete description of the sample and the conditions surrounding its taking be given, as the results of the analysis itself; and if such should become standard practice, coal-analysis would assume greater value. As it is, the published data are very confusing, and only to an extremely small extent are they really useful. The method suggested by Mr. Campbell, however, cannot have a general application; for example, in the Eastern Interior coal-basin, particularly at the present time, the output consists largely in grades other than mine-run, which in Illinois, for the year 1905, was only about 24 per cent. of the total product; and inasmuch as Mr. Campbell's method of sampling cannot give values for any other grade than mine-run, my contention that, at best, it can have but a limited application, is apparent. To illustrate the argument, there are two coal-seams, with the characteristics of which I am particularly familiar; each seam, as it lies in the ground, contains almost exactly 10 per cent. of ash; the lump coal from one of these seams ranges from 10 to 11 per cent. of ash, but from the other seam it does not average more than 6 per cent., although, as before mentioned, the average percentage of ash in the full seam is the same for each case. A careful and proper sampling of coal-seams, to be followed by analyeis, is to be commended in connection with all investigation; in fact, it should precede any careful study. A serious error, however, may be made in attempting to use such results to set values on the product as shipped or received. The only

Jan 1, 1906

By J. N. Sicking, F. H. Brinkman

A new method for obtaining equilibrium vaporization ratios (K-values) for reservoir fluids has been developed and tested. By application of the method, complex experimental measurements of liquid and vapor phase compositions are eliminated. This simplified technique reduces the cost of experimental equilibrium-ratio data for reservoir studies of condensates and volatile crude-oil systems. The method is designed for systems of constant composition and, therefore, is best suited for depletion studies where compositional changes at high pressures are minor. The basic data required, in addition to the composition of the initial reservoir fluid, are the relative vapor-liquid volumes and densities at reservoir temperature and variom reservoir pressures. Tests demonstrated that the method predicts equilibrium ratios accurately for condensates. A single test on a crude oil was not conclusive; further testing will be necessary before the accuracy of the method can be determined for crude-oil systems. In addition to determining equilibrium ratios, the calculation method provides information on the physical properties of the "plus" component in the vapor and liquid phases. The "plus" component is that mixture of components heavier than the least volatile fraction analyzed. This information is useful in studies of both natural depletion and cycling operations for condensate reservoirs where the heptanes-plus component in the gas phase is produced from the reservoir. INTRODUCTION As more volatile oil and condensate reservoirs are found, the use of phase behavior techniques to predict their performance is increasing in importance. These techniques have long been used for condensate fields and have more recently been applied to crude-oil fields containing oils of medium-to-high volatility. In these phase behavior methods, equilibrium ratios (K-values) are used to predict compositional changes in the reservoir fluids—thereby accounting for the recoverable oil that exists in the gas phase. The reliability of the predictions depends to a large extent on the equilibrium ratios used. These values must be obtained for each component for the entire pressure range being investigated. Unfortunately, because of the complex nature of hydrocarbon mixtures, accurate K-values are hard to obtain. The equilibrium ratios for a particular component will vary not only with the temperature and pressure, but also with over-all composition of the system. The importance of composition is quite critical at elevated pressures, but becomes negligible at pressures below about 300 psia. Therefore, because most phase behavior problems involve the high-pressure region, each fluid system becomes a special case. Experimental programs to determine characteristic K-values are quite difficult and time-consuming. Thus, it is often necessary to resort to approximations of the K-value data. Charts giving K-values for various mixtures and classes of mixtures are available in the literature. However, there are two major difficulties in using them: (1) the K-values of the "plus" component (that mixture of components heavier than the last one analyzed) must be obtained by extrapolation from the K-values of the other components; and (2) the K-values obtained must finally be adjusted by trial and error to agree with observed volumetric data. To eliminate these difficulties, a new method of determining equilibrium ratios was developed. Briefly, after the composition of the system as a whole has been analyzed, the method uses empirical correlations and the gross fluid properties of the system (relative vapor-liquid volumes and densities) to calculate K-values. Because the calculative procedure is long, it is best solved on a digital computer. About one hour of machine time on an IBM 650 computer is required to develop a K-chart for the fluid being examined. DEVELOPMENT OF THE METHOD OF OBTAINING K-VALUES Equilibrium ratios are defined as the ratio of the mole fraction of a component in the vapor phase to its mole fraction in the liquid phase. This statement is expressed in Eq. 1. A typical plot of equilibrium ratios for a particular system is shown in Fig. 1. It should be noted that, at pressures near the saturation pressure, the K-values appear to converge to a common point. This apparent convergence point is called the convergence pressure and is a characteristic of the system involved. Various empirical correlations of K-values have been noted. It has been observed that an isothermal plot of

By J. F. Myers, F. M. Lewis

DISCUSSION L. E. Djingheuzian (Canadian Dept. of Mines and Technical Surveys, Ottawa)—In their Summary the authors say: "Reconciling the grinding efficiency with good metallurgy is still a problem." In the discussion of the first paper8 in his reply to W. I. Garms, Mr. Myers states: "Our grinding process with smooth I-in. balls has reduced by nearly one half the metallic losses in the fine micron sizes of the tailing. This is simply because less of the fine micron sizes are produced. Since the + 65 mesh size is the same as formerly, a higher percentage of the intermediate sizes are developed. These sizes have the highest floatability, require the least reagents, and use less floating time. "These factors contribute so heavily to the overall economies that dropping our power grinding gain from 28 pct back to 19 pct is a small detail. However, we feel that this is only a momentary situation and that eventually the best features of the grinding and flotation processes can be brought together, which is as it should be." Italics are mine. The above statements, to me, appear to be the answer to the opening statement in the Summary. Denoting the costs at different power grinding gains as: Power Grinding Power Grinding Gain, 28 Pct Gala, 19 Pct Cost of grinding G G1 Cost of flotation F F1 Value of metallic losses T T1 where G1 > G2 F3 < F, and T1 < T, we have: G1+Fl+T1<G +F+T. Since the authors accept the idea that "grinding in flotation plants becomes part of the &apos;conditioning&apos; of the feed to flotation",4 i.e., that in flotation the ball mill is primarily a conditioning machine, it can be postulated that Tennessee Copper grinding at cost G1 is more efficient than grinding at lower cost G. This can be directly inferred from the Conclusion of the paper. Mr. Myers also emphasizes this at the end of his reply to Mr. Garms: "that grinding is for the purpose of preparing flotation feed and not grinding per se." This, to me, in the final analysis means that when the efficiency of grinding is weighted against the conditioning factor, the former becomes a function of efficient conditioning, hence, within the system in which proper conditioning is the dominant factor, the best grinding efficiency is provided by grinding which will contribute towards the optimum conditioning. This brings us again to the statement: "that if every grinding unit were considered as a conditioner for each following step, efficient grinding plants would become much easier to design."&apos; In other words, grinding equipment should be balanced against the flotation equipment and against chemical reactions taking place in the system. F. C. Bond (Allis-Chalmers Mfg. Co., Milwaukee)— The authors&apos; discussion of the probable ball motion in a slow speed high dilution mill is very interesting. When the 1-in. balls have worn down to about one fourth of their original weight they apparently first develop a flat surface; as wear progresses this flat face becomes concave, and other concave faces appear. It seems more probable that the first flat face may form at the softest part of the ball surface, and that each succeeding contact tends to force this flat face into sliding contact with a larger round ball; than that the flat faced ball tends to pair off with a particular round ball and to travel with it continuously. When the small worn ball has a flat face and is in sliding contact with a large round ball, the surrounding large balls will assume a more or less definite pattern, and slide against the worn ball, thus producing secondary concave faces. The primary concave face seems to be larger and better developed than the secondary faces. The ball charge can be divided into "concaves" which show at least one concave surface, "intermediates" which have developed flats or incipient concaves, and "rounds." Ball slippage is always present in a tumbling mill, and the mutual ball movement is necessarily a combination of rolling and sliding. The sliding motion is apparently concentrated upon the smaller worn balls which nest between the surrounding larger round balls. When each worn ball starts its upward path in the mill its primary flat or concave surface fits against a larger round ball, and the round ball slides upon it. The action may be something like that of the ball separator in a ball bearing, except that the worn sliding balls are always under considerable pressure. The material is ground under the combined influence of breakage 1—by impacts between falling balls and between falling and supported balls, 2—by being nipped between rolling balls, and 3—by being rubbed between the sliding balls. The rubbing action will be increased in the presence of worn balls with concave surfaces. The rubbing action probably produces a considerable portion of the finely ground slimes in the product. The worn balls commonly approach tetrahedrons in shape, and are very different from concavex, each of which has two equal opposed concave surfaces. Concavex were designed only to grind upon themselves, and not for use in combination with grinding balls. Their action in a grinding charge is very different from

Jan 1, 1952

ALEXANDER BRYDEN Alexander Bryden, clean of engineers in the anthracite mining field, and a member of the pioneer Pittston family, was claimed by death Wednesday, September 26, 1917. The announcement was not a surprise, as he had been in a critical condition for several days. Mr. Bryden had been in failing health for a year past, but his indomitable will kept him at his accustomed duties until quite recently. Two weeks before his death he attended the regular weekly meeting of the Board of Directors of the Miners&apos; Savings Bank in Pittston, Pa. At that time he apparently felt that his end was fast approaching, as he bade farewell to his associates on the bank board. Until a few days before the end, he continued to give attention to business matters at his home, in preparation for the end, which he met unflinchingly. In the passing of Mr. Bryden, northeastern Pennsylvania loses one of the best-known mining engineers, and the community, a man who, throughout his long life, was actively interested in its social welfare and business prosperity. He was for many years prominent in the management of the mining operations of the Pennsylvania Coal Co., and at the time of his death held the position of consulting engineer of the Pennsylvania and Hillside Coal. Companies.

Jan 12, 1917

Advantages to Members of Our Advertising Section.-It is our intention to make the advertising section of the Bulletin as comprehensive as possible, so that members can turn to it for complete information as to where to buy the best mining and metallurgical supplies at the lowest prices. No firms or supplies of dubious reputation are advertised in the Bulletin. If members, in buying any material, will refer to the advertisement of that material in the Bulletin, or if they do not find it advertised in the Bulletin, will, when ordering, ask the manufacturers why the goods were not advertised in the Institute publication, it will be of material benefit to all of us, because the chief reason why advertisers are unable to trace direct results is because purchasers do not mention the Bulletin when writing. Finally, if members, when in need of anything whatsoever, will write to the Institute headquarters, an effort will be made to send them a complete list of manufacturers able to supply the desired materials of good quality. The furnishing of these lists will be a benefit to our Advertising Department, as well as to the members. We need scarcely call attention to the advantages obtained by the members from the money which advertising brings in, because all this money is returned directly to the members in one form or another.

Jan 7, 1913

Advantages to Members of Our Advertising Section.-It is our intention to make the advertising section of the Bulletin as comprehensive as possible, so that members can turn to it for complete information as to where to buy the best mining and metallurgical supplies at the lowest prices. No firms or supplies of dubious reputation are advertised in the Bulletin.. If members, in buying any material, will refer to the advertisement of that material in the Bulletin, or if they do not find it advertised in the Bulletin, will, when ordering, ask the manufacturers why the goods were not advertised in the Institute publication, it will be of material benefit to all of us, because the chief reason why advertisers .are unable to trace direct results is because purchasers do not mention the Bulletin when writing. Finally, if members, when in need of anything whatsoever, will write to the Institute headquarters, an effort will be made to send them a complete list of manufacturers able to supply the desired materials of good quality. The furnishing of these lists will be a benefit to our Advertising Department, as well as to the members. We need .scarcely call attention to the advantages obtained by the members from the motley which advertising brings in, because all this money is returned directly to the members in one form or another.

Jan 7, 1913

By Sidney H. Loram

As the work carried on by this Company, of which the writer has been in charge for the past two years, is somewhat unique, the following account of it may be of interest, and, on that account, is offered to the Institute without any attempt to claim this practice as the best. Mines. The mines supplying ore to the Company arc situated in three groups: the Guanaco field,.about 80 miles N.E. of the port of Taltal (lat. 25" S., long. 70" 30&apos; W. of Greenwich); the Sierra Overa, about 63 miles S.W. of Taltal; and Paranao, about 42 miles due N. of Taltal (12 miles N. of the small town of Paposo, once famous for its copper-output). Guanaco. This field lies in the center of an absolutely waterless mountainous desert, where not a sign of vegetation can be found for miles. The dryness is such that ivory and horn crack and open, while raw-hide must be used in place of leather, which -would become worthless in a very short time. Water is brought about 21 miles by piping from the Cordillera, but only in small quantities, and costs in the Guanaco $7 (= $1.78 gold) per cubic meter. All supplies and food are sent from the port of Taltal, which in turn draws its supplies from the south of Chile, the

Jan 1, 1900

By Paul L. Russell

Of the potential applications of nuclear explosives to mining, excavation is perhaps the most obvious and the best understood, and probably the most practical for use in the near future. Large quantities of rock and earth can be moved by proper emplacement of nuclear explosives, but economic and practical relationship must be determined between the known capabilities of nuclear explosives and the required excavating to remove overburden. On an energy yield basis, even the cheapest of the present commercial explosives cost more than the most expensive nuclear explosive. Comparing the energy yield of a megaton thermonuclear device with the yield of TNT shows that one energy yield per dollar is 400 times greater for the thermonuclear device. However, small-yield nuclear devices (a few 10&apos;s of kilotons yield) are less efficient blasting materials than chemical explosives, with the result that the heat of explosion is utilized less effectively. While only 1 lb of conventional explosive is required to excavate 1 cu yd of rock, or about 2 million cu yd per kiloton, nuclear devices excavate from 100,000 to 300,000 cu yd per kiloton. This changes the economic situation, and it is thus apparent that nuclear explosives are cheaper only for the large explosions.

Jan 6, 1964

By Thos Egleston

The sands of Snake River, Idaho, have long been known to contain gold. They were worked by some of the first prospectors who came to Idaho, and on the banks still stand the ruins of camps abandoned for years. There are almost always prospectors searching for gold during the season of low water, and it is not an infrequent thing to find a miner of the old type actually panning the sand, or the prospect-hole which he has just left. There is more or less mystery about these miners and their methods of finding the spots where they work. They are always subjects of much speculation to the ordinary traveller. The rich discoveries are, for the best of reasons, concealed until the claims can be taken up. It is difficult to find a place where there are no prospects, but the " colors " are so very fine that they do not offer much inducement to enterprise. The California miner usually values a color at from 5 to 10 cents, often the latter; while on Snake River it would take 100 colors, or even more, to make that amount.

Jan 1, 1890

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,&apos; to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.&apos; These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken&apos;s Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By Fred D. DeVaney

DURING the past few years a radically new process for the magnetic roasting of iron ores has been investigated and developed by Pickands Mather & Co. and the Erie Mining Co. in the Erie laboratory at Hibbing, Minn. This process, originally devised by Dr. P. H. Royster of Washington, D. C., involves the use of a roasting technique quite different from older methods. It has now been demonstrated that iron-bearing materials can be roasted as effectively as by any previously known method, and at a much lower cost. The increasing shortage of highgrade iron ores in this country has accelerated the search for new methods that would permit low grade materials to be utilized. The concept of magnetically roasting low grade nonmagnetic ores such as the oxidized taconites and then separating such material magnetically has always had considerable appeal. The magnetic concentration idea is attractive because of the sharpness of the separations and cheapness of the method. Heretofore, however, the equipment and the processes available for the magnetizing-roasting -step have left much to be desired. The customary equipment available for reduction roasting has been: 1-multiple hearth furnaces, 2-rotary kilns, and 3-shaft type kilns. In addition, it is understood that some work has been done in magnetically roasting fine ores by a process using the FluoSolids principle, but little information on this process is available. The multiple hearth kiln has been used the most but first costs and operating costs have been high because of low capacity, high maintenance, and poor gas utilization. Magnetic roasting can be done in a rotary kiln, but the radiation losses are high and the conversion to magnetite is usually unsatisfactory because of poor contact between the gases and the solids. Of the shaft-type furnaces, probably the most efficient yet developed is that designed by E. W. Davis of the Minnesota Mines Experiment Station. This furnace was operated at Cooley, Minn., during 1934-1937 but was abandoned in 1937 because the operation was uneconomic. Heretofore the basic concept behind most magnetic roasting processes has been the idea of heating iron ore to a temperature of 800° to 1100 °F in a strong reducing atmosphere, preferably either carbon monoxide or hydrogen. Temperatures under 800°F were undesirable since excessive roasting time was required. Temperatures over 1100°F were avoided because of the danger of converting part of the iron to ferrous oxide which is nonmagnetic. In the new roasting process, the operation is carried on in a shaft furnace using a controlled atmosphere containing a low percentage of reducing gas. The temperature in the roasting zone is considerably higher than with the usual reducing gas and this speeds up the reduction time. Portions of the spent furnace gases are cooled and recirculated and this together with the good contact between ore and gas makes for high reducing gas utilization. High heat economy is secured by recuperating heat from the roasted ore by passing the cold reducing gases countercurrent to flow of ore. The heat transfer principle is similar to that employed in a pebble stove and to that used in the Erie Mining Co. furnace at Aurora, Minn., for pelletizing fine magnetite concentrates derived from taconite. The theory of controlled atmosphere during the roasting operation can best be appreciated by inspecting the equilibrium diagram of the Fe-C-O system shown in Fig. 1. An inspection of this diagram shows that in certain areas magnetite, Fe3O4, is the only stable form of iron. A further inspection of this table shows that if the proper ratio is maintained between carbon dioxide to carbon monoxide, such a gas will be reducing with respect to hematite, Fe2O3, and will be oxidizing with respect to both ferrous oxide, FeO, and iron, Fe. It should be kept in mind that the formation of ferrous oxide in a roasting operation is harmful, since this oxide is nonmagnetic; if it forms in any quantity, it will cause substantial loss of iron in the ensuing magnetic separation step. If a ratio of approximately three parts carbon dioxide to one of carbon monoxide is maintained, the resulting operation can be carried on at a relatively high temperature without fear of over-reduction. Specifically, most of the tests in the Erie furnace have been made at a temperature of 1500° to 1600°F, with an entrant gas containing approximately 5 pct carbon monoxide and 15 pct carbon dioxide, with the remainder largely nitrogen. It should be remembered that the ratios of carbon monoxide to carbon dioxide shown in Fig. 1 hold even though the bulk of the gas is an inert gas such as nitrogen. It may surprise many to learn that a gas containing as low as 3 pct carbon monoxide, and 12 pct carbon dioxide with the remainder nitrogen is an extremely effective reducing gas in the 1000° to 1600°F temperature range. The reducing gas is not limited to carbon monoxide, and mixtures of hydrogen and carbon monoxide may be used effectively, provided that a similar ratio is maintained between the reducing gases and carbon dioxide and water vapor. For a more detailed explanation of the theory involved, the reader is referred to U. S. patents 2,528,552 and 2,528,553. From a safety standpoint, the weak reducing gas used in the furnace offers an advantage. Its composition is such that it is well below the limits of explosion should air enter a hot furnace. This condition is not true with the usual reducing furnace, in which a gas rich in carbon monoxide or hydrogen is used. The general furnace design and method of operation may best be understood by an inspection of

Jan 1, 1952

By Orville R. Lyons

DISCUSSION Judson S. Hubbard (The Humphreys Investment Co., Denver)—In this very interesting paper several brief references are made to the Humphreys spiral, a device used for cleaning fine coal. In Table I, Plants 76 and 77, data are given on spiral performance treating Raton and Trinidad coal. The fine coal, as fed to the spiral in these instances, is actually a table middling, hence the more easily treated material was previously removed and a large number of particles were present which were difficult to clean. Mr. W. M. Bertholf of the Colorado Fuel and Iron Co. presented a paper in February, 1946, Cleaning Table Middlings from a Coal Washery with the Humphreys Spiral Concentrator, from which I quote: "In considering the results of our tests it should be noted that the feed was our table middling, and that any real separation is a &apos;moral victory&apos; as there is little material that could properly be called coal and practically no heavy rock, the consequences being that previous attempts to clean the middling have not at all been successful." Referring again to Table I, Plants 72, 73, 74, and 75, these data were obtained by Yancey and Geer and others and presented at the February 1950 Meeting, AIME, in a paper entitled Laboratory Performance Tests of the Humphreys Spiral as a Cleaner of Fine Coal. Results shown for those tests involve all particles from 8 mesh through the colloids, which admittedly is not an ideal situation for spiral feed if much refuse is contained in the —80 mesh or —100 mesh size range. As an illustration of the effect of treating too broad a size range, let us consider Plant No. 75, Kentucky No. 9 seam. Spiral feed was 8 mesh x 0. Now had this been 8x100 mesh the percentage of misplaced material would have been 8.0 pct instead of the reported 15.26 pct. Similar comparisons can be made on the other data presented with respect to the spiral. Other types of equipment show a similar trend in that whenever too fine a size is treated in a given unit process the percentage of misplaced material increases. Since the spiral is working near the finer end of the size range, it will sometimes be advantageous to treat the entire range of —8 mesh material rather than to deslime and make a fair showing on, say, the +80 or + I00 mesh. Desliming is subsequently done in any case in the dewatering or thickening operation. Results obtained by spiraling any given coal depend on factors too numerous and complex to discuss here, but there are strong indications that proper preparation of feed to the spiral can improve results obtained on some of the raw coals tested. This is clearly pointed out at the end of the aforementioned paper by Yancey and Geer. "The spiral is an extremely simple device which involves no moving parts and is constructed almost entirely of unmachined castings. Since it is such an uncomplicated mechanism, operation is simple and virtually foolproof. These characteristics, which go far toward insuring low cost operation, are attractive attributes in any coal cleaning unit." Certain equipment used in conjunction with the spiral has resulted in a decrease in the percentage of misplaced material, notably in actual practice the launder screen which is used to remove objectionable high ash fines from a spiral-washed coal product. Private correspondence with the U. S. Bureau of Mines has intimated that an additional yield of coal is possible by flotation of the spiral middling. Possible future improvements and developments may result from other methods now under consideration. Finally, some compromise must be made between the best metallurgical performance and the best practical or economical results. Mr. Lyons emphasizes in his summary this objective of overall economy in selection of equipment. G. B. Walker (American Cyanamid Co., Stamford, Conn.)—I had the pleasure of reviewing the draft of this paper and my curiosity was aroused by the data given for Tromp plants, in that all of the examples shown appeared to be 2-product separations, whereas all the Tromp plants with which I am familiar have been 3-product units. The data given for plants No. 101 and 102 appear to be taken from Tromp&apos;s brochure on his process and represent the results obtained at the Dominale plant in Holland which was operated for many years by Mr. Tromp. The plant, which was designed to treat 58 tons per hr, was sampled while treating 35 tons per hr of 3Y4x-in. coal. Example 101 appears to conform to what would result if the middling product were calculated into the refuse product, while Example 102 represents the calculation of the middling into the coal product. It is believed that Examples 103 and 104 represent the operation of the Willem-Sophie Mine in Holland recalculated on the same basis. In checking the English examples given by numbers 14, 15, 16, and 17, the same procedure seems to have been followed. These results have, apparently, been taken from an article in Colliery Engineering in August 1941, describing the initial operation of the Williamthorpe Colliery of the Hardwick Colliery Co. Two vessels are employed in this plant, one to treat soft coal and one to treat hard coal. Example No. 14 presents the results that could be obtained from the soft coal bath if the middling were calculated into the refuse, and Example 15 the results when the middling is calculated into the coal. Examples 16 and 17 represent the same expedient in the case of the hard coal bath. Of interest to this discussion is the fact that during the past year the Simon-Carves Engineering Co. in England has installed in the Williamthorpe plant their new "Sim-Car" medium cleaning system which is based on magnetic extraction and control and which is licensed under the Heavy-Media Separation Processes patents by the American Zinc, Lead and Smelting Co. This system has been described in the December 1951, issue of Colliery Engineering. It is reported that since the Williamthorpe Colliery was changed from the Tromp system of medium cleaning to the Magneto-Motive method of medium control the opera-

Jan 1, 1953

By Orville R. Lyons

DISCUSSION Judson S. Hubbard (The Humphreys Investment Co., Denver)—In this very interesting paper several brief references are made to the Humphreys spiral, a device used for cleaning fine coal. In Table I, Plants 76 and 77, data are given on spiral performance treating Raton and Trinidad coal. The fine coal, as fed to the spiral in these instances, is actually a table middling, hence the more easily treated material was previously removed and a large number of particles were present which were difficult to clean. Mr. W. M. Bertholf of the Colorado Fuel and Iron Co. presented a paper in February, 1946, Cleaning Table Middlings from a Coal Washery with the Humphreys Spiral Concentrator, from which I quote: "In considering the results of our tests it should be noted that the feed was our table middling, and that any real separation is a &apos;moral victory&apos; as there is little material that could properly be called coal and practically no heavy rock, the consequences being that previous attempts to clean the middling have not at all been successful." Referring again to Table I, Plants 72, 73, 74, and 75, these data were obtained by Yancey and Geer and others and presented at the February 1950 Meeting, AIME, in a paper entitled Laboratory Performance Tests of the Humphreys Spiral as a Cleaner of Fine Coal. Results shown for those tests involve all particles from 8 mesh through the colloids, which admittedly is not an ideal situation for spiral feed if much refuse is contained in the —80 mesh or —100 mesh size range. As an illustration of the effect of treating too broad a size range, let us consider Plant No. 75, Kentucky No. 9 seam. Spiral feed was 8 mesh x 0. Now had this been 8x100 mesh the percentage of misplaced material would have been 8.0 pct instead of the reported 15.26 pct. Similar comparisons can be made on the other data presented with respect to the spiral. Other types of equipment show a similar trend in that whenever too fine a size is treated in a given unit process the percentage of misplaced material increases. Since the spiral is working near the finer end of the size range, it will sometimes be advantageous to treat the entire range of —8 mesh material rather than to deslime and make a fair showing on, say, the +80 or + I00 mesh. Desliming is subsequently done in any case in the dewatering or thickening operation. Results obtained by spiraling any given coal depend on factors too numerous and complex to discuss here, but there are strong indications that proper preparation of feed to the spiral can improve results obtained on some of the raw coals tested. This is clearly pointed out at the end of the aforementioned paper by Yancey and Geer. "The spiral is an extremely simple device which involves no moving parts and is constructed almost entirely of unmachined castings. Since it is such an uncomplicated mechanism, operation is simple and virtually foolproof. These characteristics, which go far toward insuring low cost operation, are attractive attributes in any coal cleaning unit." Certain equipment used in conjunction with the spiral has resulted in a decrease in the percentage of misplaced material, notably in actual practice the launder screen which is used to remove objectionable high ash fines from a spiral-washed coal product. Private correspondence with the U. S. Bureau of Mines has intimated that an additional yield of coal is possible by flotation of the spiral middling. Possible future improvements and developments may result from other methods now under consideration. Finally, some compromise must be made between the best metallurgical performance and the best practical or economical results. Mr. Lyons emphasizes in his summary this objective of overall economy in selection of equipment. G. B. Walker (American Cyanamid Co., Stamford, Conn.)—I had the pleasure of reviewing the draft of this paper and my curiosity was aroused by the data given for Tromp plants, in that all of the examples shown appeared to be 2-product separations, whereas all the Tromp plants with which I am familiar have been 3-product units. The data given for plants No. 101 and 102 appear to be taken from Tromp&apos;s brochure on his process and represent the results obtained at the Dominale plant in Holland which was operated for many years by Mr. Tromp. The plant, which was designed to treat 58 tons per hr, was sampled while treating 35 tons per hr of 3Y4x-in. coal. Example 101 appears to conform to what would result if the middling product were calculated into the refuse product, while Example 102 represents the calculation of the middling into the coal product. It is believed that Examples 103 and 104 represent the operation of the Willem-Sophie Mine in Holland recalculated on the same basis. In checking the English examples given by numbers 14, 15, 16, and 17, the same procedure seems to have been followed. These results have, apparently, been taken from an article in Colliery Engineering in August 1941, describing the initial operation of the Williamthorpe Colliery of the Hardwick Colliery Co. Two vessels are employed in this plant, one to treat soft coal and one to treat hard coal. Example No. 14 presents the results that could be obtained from the soft coal bath if the middling were calculated into the refuse, and Example 15 the results when the middling is calculated into the coal. Examples 16 and 17 represent the same expedient in the case of the hard coal bath. Of interest to this discussion is the fact that during the past year the Simon-Carves Engineering Co. in England has installed in the Williamthorpe plant their new "Sim-Car" medium cleaning system which is based on magnetic extraction and control and which is licensed under the Heavy-Media Separation Processes patents by the American Zinc, Lead and Smelting Co. This system has been described in the December 1951, issue of Colliery Engineering. It is reported that since the Williamthorpe Colliery was changed from the Tromp system of medium cleaning to the Magneto-Motive method of medium control the opera-

Jan 1, 1953

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.&apos;3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By V. Koump, T. F. Perzak, R. G. Olsson

Jan 1, 1965

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members.) Engineer of many years&apos; experience in mining engineering, construction, public works, contracting, water-power development and operation, having heretofore retired on a sufficient competence, wishes to have employment with thoroughly reputable concern where his experience would be of value; the question of remuneration is of secondary importance. A-2591. Engineer, in military service nearly two years, desires, when discharged, to secure permanent position offering future opportunities. Experienced as mechanical and metallurgical engineer, investigator, teacher. Technical graduate and post-graduate from two of best American schools. Ability as executive, organizer and industrial leader. Especially fitted for industrial position of administrative nature or as technical assistant to industrial manager. Salary expected $4500 to $5000. A-2619. Member A. I. M. E., age 36, twelve years&apos; experience in smelting and hydrometallurgy of copper ores, desires research or works position with responsible company. Speaks fair Spanish. Can handle men. Will welcome difficult metallurgical problems. Salary $5000. A-2627. Mining engineer, recently discharged from the Army as Captain, Engineers, age 38, 15 years&apos; experience in the Southwest and in Mexico in gold, silver and copper mining, engineering, surveying, sampling and assaying, with special training in prospect and mine examination and the development of prospects. Speaks Spanish; immediately available; references. A-2136.

Jan 6, 1919