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By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800' and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,',' in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By Robert S. Young

During the last quarter-century, exploration for metallic deposits in Maine has been sporadic with peaks generally coinciding with periods of high metal prices. Known cases of regional or semi-regional evaluations are few; most efforts have been local and usually intensive. On the basis of broad geologic groups, the State has been divided into five fundamental environments: ( 1) coastal metamorphic belt; (2) southern volcanic belt; (3) Silurian slate belt; ( 4) northern volcanic belt; and ( 5) Devonian slate belt. Although not restricted to these areas, exploration in recent years has been concentrated in the northern and southern volcanic belts. Notable examples of recent exploration activity, directed to sulfide minerals, include: ( 1) the Knox County nickel-copper-bearing ultramafic rocks; (2) the Harborside (Cape Rosier) copper-zinc deposit; (3) the Second Pond (Black Hawk) zinc-copper-lead-silver deposit; ( 4) the Big Hill-Barrett lead-zincsilver- copper-gold zones; (5) the Parmachenee copper-zinc belt; ( 6) the Moxie Lake nickeliferous peridotite; and (7) the Attean quartzmonzonite molybdenum-copper occurrences. The Second Pond and Harborside prospects appear to be close to production. Systematic investigations for non-metallic deposits appear to have been aimed principally toward limestone, asbestos, diatomaceous earth, and spodumene-bearing pegmatites. Advances in prospecting methods, high metal prices, a favorable business outlook, increasing cooperation from large landholders, and some discoveries support the probability of increased exploration activity in Maine during the coming decade.

Jan 1, 1968

By Donald H. McLaughlin

ZEST in the search for new supplies of metallic ores and petroleum is difficult to maintain with stocks of raw materials accumulating and with over- production rightly or wrongly blamed for most of our industrial troubles. Enthusiasm over new methods of prospecting has consequently diminished and exploration programs in many fields have been drastically cur- tailed. Very naturally the effects have been felt with particular keeness in highly specialized phases of the work, such as geophysical prospecting, for the feverish scramble for new areas in which to drill beneath magnetic or electrical anomalies has abated, and there is even a lull in the firing in the battle over salt domes on the Gulf Coast. It is unquestionably an unhappy time for many of the organizations dependent on this work, but in certain respects the situation may be beneficial in correcting unsound practices that .have grown up through the necessity for haste and for quick decisions. With the restriction of the field to the more competent workers by the harsh rule of survival of the fittest, a general improvement, not only in technique but in business methods, can be expected which may go far in restoring public confidence. Geophysical prospecting in the short period that it has been utilized in North America, has suffered severely both from over-popularity and from excessive abuse. The former evil now

Jan 1, 1931

By George J. Young

(San Francisco meeting, October, 1911.) THE nature of slimes handled in the treatment of gold- and silver-ores has been discussed in technical literature to a considerable extent. The subject of slime-filtration from the practical worker's stand-point has also received much comment, and scattered through the literature of the subject are descriptions of many slime-filtration installations. Articles of this nature serve a valuable purpose and assist materially in the design of new and the improvement of old plants. The subject of the physics of slime-filtration has been touched upon to only a slight extent. The underlying principles are worthy of more intensive study and experimentation than they have received, and the main purpose of this paper is to present the results of such study and experimental work as will serve to make clear in part at least many of the principles which control the filtration of slime. Nature of Slime. Much has bean written concerning an accurate definition of the term ? slime," but no comprehensive definition seems to be generally accepted. The reason for this is clear. A slime consists of at least three different substances, each, when separated, possessing distinctly different physical and to a certain extent chemical properties. These substances are extremely fine sand, a colloidal material which may be and generally is in a coagulated condition, and a colloidal material which is in a non-coagulated condition. Suspending a slime in a relatively large volume of water by shaking and allowing sedimentation to take place, results in the fine sand settling out with comparative rapidity, followed by the coagulated material, which settles much more slowly and finally a certain portion remains

Nov 1, 1911

By Kenneth R. Hancock

Iron oxides are unique in that they are the only significant colored mineral found in a natural state suitable for use as a pigment after it has been pulverized to pigmentary size. The current world production of iron oxide pig¬ments is estimated by the author to be between 450,000 and 550,000 tons based on 1969 data. The fact that highly colored natural deposits of iron ore are found throughout the world ac¬counts for its use in prehistoric man's artistic cave paintings. These early artists did not realize that they had established man's first paint test fence which now has some 20,000 years of exposure. In addition to abundance, constituting about 7 % of the earth's crust, iron oxides have the advantages of low cost, permanency, and are not toxic. Through the centuries, succeeding civilizations have utilized iron oxides as a major source for decoration and protection when coloring was desired. In the last century the chemical industry has improved on nature by developing a complete range of synthetic iron oxide pigments which surpass the pigments pro¬duced from natural iron ores in uniformity, color quality, and chemical purity. In the United States alone, the combined production of natural and synthetic iron oxides produced sales of over $28,000,000 in 1970 (Stipp, 1970). Nomenclature With the increasing importance of the syn¬thetic iron oxides it is necessary to make a distinction between the natural or mineral pig¬ments and the synthetic pigments. Natural pigments are those products which are derived from selected ores and should not be confused with iron ores mined for steel production. Iron ores that are mined for steel must be capable of being mined and reduced to iron on a com¬mercial basis. These ores are selected on the basis of iron content and processing economics. It is therefore unusual when iron ores for steel production are suitable for use as mineral pig¬ments. Natural pigment ore sources are se¬lected for their special physical-chemical prop¬erties and can command a premium price. Synthetic pigments, and in this instance iron oxides, are those pigments produced from basic chemicals. Through chemical synthesis pig¬mentary sized particles are produced as opposed to comminution, the major procedure common to all natural iron oxide pigments.

Jan 1, 1975

By JESSE L. MAURY

ONE OF the most hopeful features of the current depression is the discussion which it has en- gendered of ways and means to counteract similar recurrences in the future. 1t is widely recognized that fruitful attack will be directed toward the steady employment of labor, through which the purchasing power of this preponderant class in society will be maintained. S. A, Lewisohn's article' has presented the major factors to be considered; the physical suffering and mental torture endured by those who are deprived of income through no fault of their own, the direct economic losses' sustained in the degradation of 'great, numbers of our population and the disintegration of efficient working forces, and the prime responsibility of owners and managers.

Jan 1, 1931

By Frank Marotta, Louis B. Lesem, Frank Greytok, John J. McKetta

Although one of the primary variables in the calculation of the flowing bottom-hole pressure in gas wells from surface measurements is the temperature at any point and its distribution in the flow-string, only few experimental data are available in the literature and little attention has been given to analysis of the problem. Virtually all of the recently published methods of calculating flowing bottom-hole pressures depend on the assumption that either the temperature is constant at some average value or that the variation is linear with depth. The purposes of this work are to analyze the problem theoretically and to verify the analysis by comparison with experimental data so that practical problems in the analysis of the behavior of gas wells can be solved with greater accuracy, reliability, and ease. MATHEMATICAL OUTLINE OF PROBLEM Assuming that: 1. The mass velocity and chemical composition of the gas stream are constant and in normal gas well operations, the change in linear velocity in the entire flow-string is trivial, 2. The product of the density and heat capacity of the gas is constant, 3. No horizontal temperature gradient exists in the gas stream, 4. Net flow of heat by conduction within the formation and in the gas stream in the vertical direction is trivial in magnitude and can be neglected, 5. The regional vertical geothermal gradient is constant, and 6. The temperature of the gas entering the borehole is constant, and equal to that of the reservoir, a set of two simultaneous, linear partial differential equations with appropriate boundary conditions was derived to describe the temperature distribution in the gas stream and the surrounding formation. These equations were solved by operational techniques for the distribution of temperature in the gas stream. The resulting integrals were evaluated numerically on an IBM 604 at the Machine Accounting Div. of the Railroad Commission of Texas. DERIVATION OF FUNCTIONS FOR THE DISTRIBUTION OF TEMPERATURE The physical system is a circular hole of radius a in an infinite medium with thermal conductivity K, density p8, and heat capacity c,. Under shut-in conditions the well is in thermal equilibrium with the surroundings and the increment in temperature is given by - ?T3/L x. Gas of density pg and heat capacity c.. flows upwardly through this hole in the direction of increasing x with a linear velocity W. Writing a heat balance on an element of gas ?x in thickness, convective heat transfer + conductive heat transfer + energy required to lift a unit mass of fluid = change in energy content. pa2W po Co To - pa2Wpo Co To x+xx - 2apK?x ?T8/?r r=a - Wpa2 po?x/778 = CoPopa2?x?To/?t... Dividing by (copopa2?x) and taking the limit as ?x tends to zero, -W (?To/?x + 1/778Co) + 2 K/a Po Co ?T3/?r r=u = ?To/?t

Jan 1, 1958

By W. Luyken

A NUMBER of articles have been published, notably those by R. S. Handy, R. T. Hancock and A. P. Watt in Engineering and Mining Journal, dealing with the calculations involved in ore dressing.. These publications demonstrate both, the importance of the subject and the lack of success in developing a generally recognized method for comparing enrichment effects. Considering that we may wish -to compare enrichment results on similar or dissimilar ores, that we may desire to make the comparison on the basis of either the absolute or the economical efficiency, and that the number of factors upon which the result depends is large, the question arises whether it is possible to set up a positive method for such calculations. In the following pages it is our aim to show that a sure, complete and successful way to overcome existing difficulties has been found. GRAPHICAL ANALYSIS OF ORE-DRESSING PROCESSES The following is from Truscott's Text Book of Ore Dressing (London, 1923) x = assay of ore treated (feed). y = assay value of the concentrate. z = assay value of the tailing. a = weight of feed. b = weight of concentrate. c = weight of tailing. C = fractional concentration = b/a= x-z/y-z (1) K = ratio of concentration = 1/C = a/b =y-z/x-z (2) R = fractional recovery = yb/xa = Cy/x. (3) 100R = percentage recovery. Copt = theoretically best concentration. 100 - Copt = waste in the feed.

Jan 1, 1929

By Charles W. Perry

The options of enhanced oil recovery, coal syncrude, and shale syncrude are compared by approximately equivalent economics. The physical constraints for the major enhanced oil recovery processes are described, followed by new estimates of cost. The range for all three options in terms of light syncrude equivalent are $22 to $40 per barrel in 1980 dollars.

Jan 1, 1982

By Sidney Snook

FLUORSPAR production is the most important industry in a compact area in southern Illinois and western Kentucky bordering the Ohio River. Producers' activities do not usually figure much in the mining news of the country, so that few know that the last year or so has been an unusually active one. Mine shipments more than doubled in 1939 compared with the poor year 1938. The average price changed but little, though it is now about one-sixth higher than at the beginning of last year. The outbreak of war in Europe a year ago lent an immediate stimulus to the industry, though only about 15 per cent of the domestic consumption is normally imported, thanks to a tariff of $8.40 per ton, equivalent to about 30 per cent ad valorem. Be- cause of the increased production and many expansions and improvements in the mines and plants, the period since the beginning of 1939 has been the most important one for the industry in the last 15 years.

Jan 1, 1940

By R. E. Pray, M. C. Fuerstenau, J. D. Miller, B. F. Perinne

Quartz cannot be floated with potassium amyl xanthate as collector at any pH. Complete flotation is achieved with certain minimal additions of amyl xanthate and Pb from pH 5.8 to 8.5 and with amyl xanthate and Zn from pH 7.5 to 8.1. The active species of these metal ions responsible for activation are shown to be PbOH and ZnOH No flotation was effected when Cu and Mg were added as activators. Previous work1,2,3,4,5,6,7 has shown that quartz may be floated in the presence of sulfonate or soap when the following two criteria are met: 1) some portion of the added metal ion has hydro-lyzed to its first hydroxy complex, and 2) a precipitate of the metal-collector has formed. Since sulfonate and soap, two substantially different anionic collectors, conform to these criteria, this phenomenon may well be expected to be of a general nature. In this view then, it would appear that any anionic collector, including xanthates, should also float quartz when these two criteria are met. The object of this paper is to demonstrate the conditions under which quartz will respond to flotation in the presence of potassium amyl xanthate. EXPERIMENTAL MATERIALS AND TECHNIQUES Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Potassium amyl xanthate was selected as collector. Purification of this reagent was effected with the following method: 1) a laboratory sample of potassium amyl xanthate was dissolved to saturation in hot ethyl alcohol and filtered several times while still hot, 2) the filtrate was cooled, during which time potassium amyl xanthate crystallized out of solution; the xanthate was then separated from the solution by filtration, 3) the amyl xanthate was dissolved in fresh hot ethyl alcohol and filtered, 4) step (2) was repeated, 5) the crystalline potassium amyl xanthate was washed with ethyl ether five times, and 6) the xanthate was dried for 24 hours under continuous vacuum. Inorganic impurities are insoluble in hot ethyl alcohol whereas dixanthogen is soluble in ethyl ether. Five-gram charges of 48x150 mesh quartz were conditioned for 3 min in 125 cc of solution containing the reagents and were floated with the small-scale cell and procedure described in previous papers.478 Reagent grade HCl and NaOH were used for pH adjustment, while reagent n-amyl alcohol was added as frother. Frother addition is necessary with this technique, but it should be mentioned that data, similar to those shown in Fig. 2 for 1 x10-4 mole per liter Pb++ and 1 X 10-4 mole per liter AX-, were also obtained with a Hallimond cell in the absence of frother. EXPERIMENTAL RESULTS Clean quartz could not be floated with amyl xanthate at any pH. Flotation was achieved under certain conditions, however, when various metal ions were added to the system. The activating ions used were lead, zinc, copper and magnesium, added as reagent grade chloride salts. Lead as Activator: The effect of Pb++ as activator was examined at five different additions of amyl xanthate (Fig. 1, 2 and 3). When 1x 10-5 mole per liter xanthate was added in the presence of 1 x 10"4 mole per liter Pb ++, no flotation was obtained at pH 6.5 or below, while a recovery of about 60% was effected at pH 7. When the pH was increased to 7.8, no flotation was again obtained, Complete depression was noted from pH 7.8 to about 10, at which point a recovery of about 30% was achieved. At about pH 11, the precipitate of lead amyl xanthate which was present below this pH dissolved and complete depression occurred. When 2.5x 10-5 mole per liter xanthate was added with the same lead addition, no flotation was obtained at pH 5.8 and below, whereas a recovery of

Jan 1, 1965

By AIME AIME

WITH the example of the steel open-hearth men and their round table conference before the copper men, the query naturally arose "Why cannot we do likewise?" The advantage of pooling and comparing knowledge on smelting in the copper reverberatory furnace seems particularly pertinent at this time when all metallurgical economies possible must be rigorously enforced. A great deal of data had also been obtained and filed during the period of litigation over the Carson patent, and it would naturally be available with the cessation of further suits. With these ideas in mind, H. Foster Bain took up the advisability of holding such a conference directly with the heads of all the companies in the United States operating copper reverberatories, and found a nearly unanimous response. The mining companies appointed representatives directly, or indicated to the heads of various metallurgical operations what members of their staffs should be sent to such a conference.

Jan 1, 1930

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10' nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described' that comes close to being in the proper range.

Jan 1, 1954

By D. P. Harris

This paper surveys a few of the quantitative exploration models that might be of interest to an ex-plorationist seeking to apply methods of operations research to mineral exploration. A general development of each model is presented, and the model is evaluated relative to the exploration activity. Finally, a philosophy of exploration and mineral resources is presented, and a possible exploration strategy incorporating concepts of some of these models consistent with this philosophy is proposed. The high cost of conducting an effective exploration program has generated an increasing interest in methods of optimizing the allocation of the resources of a firm engaged in mineral exploration. As a step towards this, mathematical models have been formulated which are designed to quantify those variables of mineral exploration in such a manner that they can be integrated with all phases of the firm's operations so as to optimize its profit objective. QUANTITATIVE MODELS General: Exploration models express at least two concepts: mineral occurrence and effectiveness of search. In simplest terms, an exploration model might be formulated mathematically as follows: P(X) = F(X) . G(X), where P(X) = the unconditional probability of discovery of X deposits, F(X) = the probability of occurrence of X deposits, and G(X) = the probability of discovery of X deposits, conditional upon their existence in the search area. With these general models as a basis of reference, some of the specific exploration models are examined below. The Allais Model: DEVELOPMENT - M. Allaisl performed the first study in which a philosophy of exploration was formulated into a probability framework. His objective was to estimate the economic profitability of the exploration of the Algerian Sahara. Allais divided the Algerian Sahara into blocks of land (called cells) 10 km square and defined the random variable, X, as the number of mining districts per cell. Thus, F(X) would describe the probability of 1, 2, or n mining districts occurring within any cell of the search area. Allais reasoned that his best information as to the form of the distribution, F(X), was the number of mining districts per cell that had been found in well explored areas in the world, such as the Western States of the U.S. He found that the Poisson function produced a reasonably good fit to the distribution of districts in these explored areas: where? is a parameter, such as the average number of districts per cell. Thus, by determining the value

Jan 1, 1968

By Francis A. Thomson

DO the curricula of our mineral technology schools prepare their graduates to meet properly the full range of their responsibilities in after life? An unequivocal "no" could be returned to this question, because training and experience in professional work are quite as important as adequate college preparation. Furthermore, a had curriculum with a splendid corps of men doing the teaching and a competent body of students doing the learning will produce a better result than an ideal curriculum in the hands of unqualified teachers and poorly prepared students.

Jan 1, 1937

By John F. Wiggert

DURING the early years of Homestake operations, shaft signaling from the cage tenders to the hoisting engineers was done by mechanical means. Small steel cables or jointed steel rods were suspended in the shaft compartments and counterbalanced with weights or springs. These cables or rod strings were connected to the mechanically operated gongs at the engineers' stations by means of bell cranks and steel wires. The system was simple and economical and served the purpose well until the mine reached a depth of 1000 ft., then the system became slow and cumbersome and required a considerable amount of muscular effort to operate it with much speed, because of the inertia of the heavy moving parts. The mechanical signaling was superseded by a simple electrical system consisting of a single pair of wires in steel conduit for each shaft compartment. In the shaft at each station a pull switch was connected to the wires. The switches were operated by means of bell cords, which extended from station to station. This electrical system was a great improvement over the mechanical one, but it had one serious drawback, which also applied to the older system; namely, the engineer did not know where a signal originated. Later on this signaling was improved to overcome this drawback, and to give the engineer a positive indication of a signal's origin. In this system a separate return wire from each pull switch is carried to an annunciator at the engineer's station, where it indicates the signal's origin. While the annunciator system used by Homestake is very safe and reliable, it has the inherent drawback of all wire-connected systems in that it is impossible to send a signal from a moving cage. A number of years ago Homestake became interested in the possibility of using some sort of radio transmission for shaft signaling. The company did much experimental work with purely radio signal transmission, but no practical way was discovered to use radio transmission in a mine shaft for signaling to or from a cage. Therefore, all efforts were directed to devising a practical way of using the hoisting rope as part of the circuit. It was realized that the return circuit from the rope would need to be through electrostatic coupling between the cage and the earth or ground sides of the shaft, because the guides would not always be wet enough to make possible good electrical contact between the cage and earth, therefore relatively high-frequency alternating current was chosen as the medium of transmission. Soon a practical system was developed for transmitting an electric current from a moving cage over an electric circuit of which the hoisting rope was a part. A high-frequency electric current is used as a carrier to transmit the signals or mes-

Jan 1, 1941

By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;' Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of' the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.' In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968

By W. Crafts, J. L. Lamont

Electrolytic extraction of carbides from quenched and tempered steel and their examination under the electron microscope were found to be helpful in understanding the mechanism of secondary hardening in alloy steels1 and the same technique has been applied to isothermally transformed steels. A preliminary survey of the utility of the method has indicated that it has promising possibilities for investigating the characteristics of pearlite and bainite. The examination of a few carbon and chromium steels has suggested that pearlite is formed with carbides of two varieties representing the lamellar and nonlamellar forms and that bainite appears to form with a structure analogous to, but significantly different from, martensite. Procedure The method used for examining the carbides was similar to that described previously.1 The chromium steels used in the investigation were made from an Armco iron base in an induction furnace and were not treated with grain-refining deoxidizers. The composition of the steels is given in Table 1. Three-inch square ingots were forged and rolled to 1/8-in. thick sheet for use in the isothermal studies. After rolling, the sheets were sandblasted to remove the rolling scale. Specimens approximately 3/4-in. wide and l1/2-in. long were prepared from the 1/8-in. sheet. They were heated in a salt "bath at 2100°F (1150°C) for 1/2 hour, transferred to other salt baths at 1300°F (704°C), 1000°F (538°C), 800°F (426°C), or 600°F (315°C), held for various periods up to 100 hr and finally quenched in water. After quenching, the specimens were cut in half, one half being submitted to microscopic examination and the other half being used for the electrolytic extraction. The isothermally transformed specimens were submitted to examination under the light microscope to determine the degree of transformation and type of structure and were photographed at 2000 X. Carbide residues were obtained by electrolyzing in 10 pet hydrochloric acid and collecting the residue in glycerine to minimize attack by the acid. As pointed out in the earlier paper, the carbides are attacked to some degree during electrolysis. This attack is relatively minor on the coarser carbides but may be quite severe on the fine bainitic carbides. The residues were washed free of the glycerine with water and alcohol. The alcohol was removed by repeated washings of amyl acetate, and the amyl acetate suspensions were transferred to stoppered vials. Debye-Sherrer X ray diffraction patterns of the residues were prepared using a chromium target. A selection based on the microstructure and X ray data was then made of samples considered most illustrative of the progress of transformation. Electrolytically extracted residues from these samples were submitted to examination by W. D. Forgeng and A. C. Jenkins on the electron microscope at the Research Laboratories of The Linde Air Products Co. and electron micrographs were made at X 5000 and enlarged to 25,000 X. The micrographs obtained with both the light and the electron microscopes are mounted side by side in the accompanying figures. Although no effort was made to establish the T-T-T diagram for the chromium steels, the times for holding in the salt bath were adjusted with the intention of making the samples represent different stages in the transformation at temperatures of 600, 800, 1000, and 1300°F. The degrees of transformation and results of X ray examination are shown in Tables 2—4. The carbide designations refer to orthorhombic or trigonal carbide types and are not meant to imply that the compositions are exactly as indicated. X ray Diffraction Data The occurrence of Fe3C and Cr7C3 in these steels was found to be consistent with published data on comparable chromium steels. Steels A and B with relatively low ratios of carbon to chromium contained Cr7C3 in the pearlitic structures and FeuC in the

Jan 1, 1950

By N. V. Hansell

l. INTRODUCTION. THE last few years have shown an increasing interest in the subject of beneficiating iron-ores -in all iron-producing countries. In the United States, this movement has been slower than in certain parts of Europe, for the obvious reason that the abundance and relative cheapness of the Lake Superior iron ores has hindered the development of enterprises for the preparation of low-grade ores. Gradually, however, conditions have changed. The world's consumption of iron is increasing enormously. Being in 1900 about 40,000,000 tons, in 1910 ii was already 60,000000; and there is no reason to doubt that for the near future the increase in iron-consumption will continue at the same rapid rate, especially with, the development of China, certain parts of Africa, and other regions which have hardly been touched as yet by modern industrialism. It is. therefore, not surprising that apprehension is felt that the known available iron-ore resources of the world are gradually being depleted. Signs of this feeling are the recent investigation, under the direction of the U. S. Geological Survey, of the iron-ore resources of the United States, and the estimate presented to the last International Geological Congress, at Stockholm, Sweden, of the iron-ore resources of the world. These investigations have emphasized the fact that the known high-grade ore-deposits are limited in extent, and will, at a not distant future, be exhausted, compelling the iron industry to depend for raw material on the enormous deposits of low-grade ores which are distributed over almost all the world. The discovery of new deposits of high-grade ore, in countries not yet thoroughly explored, will not materially change this prospect. Of course, the part which such new deposits will play in the future cannot be forecast. The difficulty and cost of transportation will probably exclude many of them from use at the present centers of the iron industry.

May 1, 1912

By H. F. Gossenberger, J. J. Tietjen, J. J. Gannon, C. J. Nuese

External quantum efficiency measurements at 300" and 77°K are presented for vapor-grown GaAs and GaAs1-xPx electroluminescent diodes as a function of junction depth and doping. In GaAs, external efficiencies are found to decrease exponentially with increasing junction depth, defining an average absorption coefficient of 900 cm-1 at 300°K and 350 cm-1 at 77°Kfor epitaxial layers of p-type GaAs. It is shown that photon absorption losses dominate at room temperature and, in fact, account for most of the external efficiency degradation between 77° and 300°K. Healever, the internal ('junction) quantum efficiency is also found to decrease by a factor of 3.5 between 77" ALTHOUGH rapid progress has been made in recent years with GaAs, Gap, and their alloys for use in electroluminescent diodes, there are still important unknown factors related to the performance of these de- and 300°K. The dependence of GaAs efficiencies on donor and acceptor concentrations is presented, illustrating best efficiencies at donor concentrations of 1.5 to 2x 1018 cm-3 . External efficiencies are found to be independent of acceptor concentrations less than 3 x 1019 cm-3 but to degrade at higher doping. The fabrication of GaAsi-xPx electroluminescent diodes is briefly discussed. External efficiencies here for planar uncoated diodes are about 0.035 pct at 300°K and 0.4 pct at 77°for x = 0.42. A brightness of about 8500 ft-Lamberts is attained at 77°K and of 315 ft-Lamberts at 300° K. for curvent densities of 10 amp per sq cm. vices. For example, although the external efficiency is known to decrease by factors of typically 10 to 30 between 77°K and room temperature, the exact causes of this are still uncertain. Experimental results of ill' and carr2 with zinc-diffused electroluminescent diodes suggest that this external degradation is almost entirely due to increased absorption losses at room temperature, with a relatively temperature-independent internal efficiency; recent calculations by Gonda et al.3 corroborate this hypothesis. In contrast, Pilkuhn and Rupprecht4 find the internal efficiency of solution-grown GaAs laser diodes to degrade from 100 to 66 to 40 pct as the temperature is increased from

Jan 1, 1969