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By A. B. Parsons

AT the outset, the authors of this paper desire to file a disclaimer and an, explanation. They have no inside information from occult sources; neither of them feigns clairvoyant powers in the slightest degree. It is true that they have indicated on be graphs an approximate trend for the consumption of seven important mineral commodities up to the year 1954. At best this is a risky business; the figures do not pretend to be any- thing more than reasoned conjectures that are predicated on an attempt to evaluate some of the more obvious of the many factors that are likely to have a bearing on the future.

Jan 1, 1937

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By W. R. Ingalls

IF, in this study of the outlook for the copper industry of the United states, I find myself assuming to be prophetic in some respects I shall express myself with hesitation and with the foresight that after the end of the war with Germany the war with Japan may continue; anyway there is sure to be an uneasy period before copper and the other metals begin to flow smoothly through the natural channels of consumption. It is mainly my purpose to survey conditions and suggest some probabilities, or possibilities, rather than to prophesy. In interpreting them it will be necessary to make certain aasurnptions, among which will be (1) expectation of a rise in the general price level,, which so far has been one-sided; (2) continuance of the k. tariff on copper imports; and (3) lock-up of government-owned copper as a military re- serve. Of these assumptions the first is indicated by the lessons from economic history, and by current symptoms. The second and third depend upon political action by Congress.

Jan 1, 1944

By D. C. DERINGER

METALLURGISTS and mill operators appreciate, in a general way, .the economic or commercial relationship between recovery and grade of product but few have correlated in detail fluctuating metal prices with the metallurgy. They know that many factors such as metal price, dedusiions for returning charge, transportation, percentage of metal in head ore, etc.; all affect the commercial relationship between recovery and grade of product. In practically every mill some one at some ' time has calculated the amount of recovery that can be sacrificed for each percentage increase in grade of concentrate and from this calculated ratio the commercial or ., economic tail has been established. Such a ratio finally becomes a well-entrenched rule by which the progress of the metallurgy is judged.. When once established, these-, ratios are but seldom corrected to changes of metal prices for each possible grade of concentrate that may be produced. The calculation is tedious when often repeated. Other methods have been suggested and used to correlate the commercial with the metallurgical phase. A factor .derived ,by multiplying the grade of concentrate by recovery is often used, but is of little importance because it does not possess a single commercial quantity. The percentage monetary recovery calculated by dividing the gross value of the ore into the net smelter return gives a good economic index and, is to be commended, but it is difficult to correlate exactly and quickly the work of each day on a commercial basis.

Jan 1, 1931

By W. D. B. Motter

DURING the early development of blasting with liquid oxygen explosives the trend of experimentation was towards increasing the effectiveness of the explosive. Its characteristic of becoming inert after evaporation of the oxygen content made a strong appeal from the standpoint of safety, especially with missed holes. It later became apparent, however, with practical use of this explosive, that LOX lacked certain other safety characteristics. As its effectiveness was increased, it became more subject to detonation by impact. The object of this paper is to show the steps taken by one operating company to achieve greater safety in the large-scale handling of liquid oxygen explosives.

Jan 1, 1933

By R. W. Raymond

That the death of Martin Coryell, which occurred at Lambertville, New Jersey, on Monday morning, November 29th, touched the sympathies of a wide circle of professional associates and personal friends, was amply testified by the gathering at the funeral services on Friday. Like his distinguished friend and neighbor, the late Ashbel Welch, Mr. Coryell was one of those pioneers in American engineering to whom we owe the great railway and canal systems which lie at the base of our national prosperity, and who have consequently enjoyed the respect and esteem of their successors of the present generation. Martin Coryell was born July 20th, 1815, at New ope, Rucks County, Pa., and was educated principally in the schools of his native town arid of Lambertville, New Jersey, to which place he returned for permanent residence fifty years later. With the exception of a brief period in youth, during which, to restore his failing health, he learned and practiced for a few months the carpenter's trade, and another brief period, later in life, when he read law for a time in the office of B. H. Brewster, of Philadelphia, afterwards Attorney-General of the United States, Mr. Coryell may be said to have spent his life as an active civil and mining engineer. Even these two episodes can scarcely be said to have been deviations from that profession, since they served to give him more thorough preparation for constructive and administrative work. The Delaware Division Canal, the Raritan Canal, and the Brunswick Canal, are among those upon which Mr. Coryell was employed. For the Raritan Canal Company, under the superintendence of Ashbel Welch, he located the greater part of the Belvidere Railroad (now the Belvidere division of the Pennsylvania Railroad), and directed its construction from Trenton to Lambertville. He was also active as a mining engineer, being one of the early pioneers of mining in the Lake Superior copper region, and had much to do with the development of the Hazleton coalfield and the railroad which has since expanded into the Lehigh Valley system. In 1862, he removed to Wilkes-Barre, where, in 1864, he became manager of the Warrior Run Mining Company. One of the editors

Jan 1, 1887

By L. R. Smith

BUTANE OPERATED drilling rigs are a recent innovation in the petroleum industry, so extensive data on their operation are not available. However, experience indicates that, within limitations, as much can he accomplished with butane as with steam, at a decided reduction .in expense of installation and cost of operation. Commercial butane is a liquid motor fuel similar to gasoline, but much more volatile, so that it has to be stored under pressure. At 10° F. it is liquid at atmospheric pressure, but at 100° it has a pressure of 70 lb. or more. As soon as the pressure is reduced, it turns to vapor and in that state is far more easily mixed with the air necessary for combustion. Butane occurs as a by-product in the absorption process of natural gasoline extraction from casing-head gas. The product has been used to some extent 10 raise the octane value of gasoline. However, because of its volatile nature, such admixture is stable only to a limited degree. Attempts also have been made to introduce the product in a gaseous form into oil- hearing formations in repressuring work. It has, however, until recently, for the most part been wasted.

Jan 1, 1937

By E. Swartzman, G. C. Behnke

THE free-swelling index, a numerical value for the free-swelling properties of coal, is being used to an increasing extent in specifying coal for burning in various types of equipment. The empirical standard ASTM method for determining this index uses, as a source of heat, a gas burner which requires frequent calibration because gas pressures are not constant, relatively small changes in gas pressure resulting in rather wide variations in the temperature attained in a crucible and thus in the resultant size of the coke button. Furthermore, the quartz crucibles specified for the test are not standard equipment, and relatively small variations in dimension and wall thickness from those specified often result in rather wide variations in the resultant size of the button. A method of analysis to be satisfactory not only for a scientific laboratory but also for use in industrial control laboratories under varying conditions should employ equipment which is rugged, easily calibrated, and readily replaceable by standard materials. Gas is not universally available as is electricity, and it is generally easier to calibrate and control a simple electric furnace or heater than a gas burner, the voltage not usually fluctuating to the degree that gas pressure does. Quartz crucibles are fragile, and the size specified in the test is not normally used for any other purpose in the laboratory. Although more expensive, the 15-cc platinum crucible, available in all laboratories where volatile matter in coal is determined by the standard ASTM method, is sturdy and standard and easily replaced. Because of these considerations, a modification of the standard method has been developed which employs a standard laboratory 350-w cone heater and standard 15-cc platinum crucibles. The results of numerous tests conducted with such apparatus show conclusively that the free-swelling index values as judged by the buttons produced with this equipment are exactly the same as those obtained by the standard gas burner method. Thus it is suggested that this electric cone heater method employing standard 15-cc platinum crucibles be considered as an alternative to the ASTM method, Designation: D720-46. The free-swelling index of coal is determined by means of the ASTM method, D720-46. This method, which is an adaptation of the crucible swelling test for coal of the British Standards Institution, consists of heating 1 g of coal in a special covered quartz crucible in a regulated gas flame for a period of not less than 2.5 min in which time the temperature of the inner surface of the bottom of the crucible reaches a temperature of 82025°C. The residual coke button is then compared in size and shape with a series of standard profiles shown in Fig. 1 and designated by number from 1 to 9 in increasing order of size. As the method is empirical, it requires rigid standardization of the apparatus and repeated calibration of the gas burner. The dimensions of the low form quartz crucible recommended must be rigidly adhered to as small variations in diameter or wall thickness result in variations in the rate of heat transmission and thus in the resultant size and shape of the coke button. The gas burner must be calibrated almost every time a new set of determina-

Jan 1, 1952

By P. Barnes

The sums given in the accompanying table are those actually paid for material and labor up to about August, 1875; but, as some parts of the machinery were not wholly completed at the starting of the works in September, 1875, the statement cannot be taken as an absolutely correct note of the total cost. A complete description, with engravings of the building and machinery, was given in Engineering, April 26th, 1878, in a paper by Messrs. A. L. Holley and Lenox Smith, to which convenient reference may be made. A detailed list of the construction accounts has been given in a paper, by the present writer, in vol. vi, Transactions of the Institute. A summary is given in the table of the items in each class which enter into the total cost, and also a note of the proportion which each of these items forms of the whole. A concise view may thus he obtained of the facts embodied in the statement as a whole, even though it cannot lay claim to completeness in showing the entire or final cost. An urgent suggestion has reached the writer from a distant country that such statements of cost to be really most serviceable should give the details in days of labor, in weight of iron, and in number of brick, and to this an assent is most cordially yielded. It is true, however, that the mere labor of copying arid compiling these details to such a degree of minuteness, would be very great, and, in any event, the probable difference between the plans of an existing establishment and one projected, would be so wide as to render even so complete a statement of cost of little more real service than the approximate notes given herewith.

Jan 1, 1879

By P. Barnes

THE sums given in the accompanying table are those actually paid for material and labor up to about August, 1875; but, as some parts of the machinery were not wholly completed at the starting of the works in September, 1875, the statement cannot be taken as an absolutely correct note of the total cost. A complete description, with engravings of the building and machinery, was given in Engineering, April 26th, 1878, in a paper by Messrs. A. L. Holley and Lenox Smith, to which convenient reference may be made. A detailed list of the construction accounts has been given in a paper, by the present writer, in vol. vi, Transactions of the Institute. A summary is given in the table of the items in each class which enter into the total cost, and also a note of the proportion which each of these items forms of the whole. A concise view may thus be obtained of the facts embodied in the statement, as a whole, even though it cannot lay claim to completeness in showing the entire or final cost. An urgent suggestion has reached the writer from a distant country that such statements of cost to be really most serviceable should give the details in days of labor, in weight of iron, and in number of brick, and to this an assent is most cordially yielded. It is true, however, that the mere labor of copying and compiling these details to such a degree of minuteness, would be very great, and, in any event, the probable difference between the plans of an existing establishment and one projected, would be so wide as to render even so complete a statement of cost of little more real service than the approximate notes given herewith.

Jan 1, 1879

By Noel Cunningham

MANY excellent descriptions of the mills of the, Porcupine district have been written, but no discussion exclusively devoted to the metallurgical technology has been given. These notes are intended to cover this feature briefly. They are based upon 2 ½ years' mill operation in the district-i.e., practically since the beginning of metallurgical operations. Character of the Porcupine Ore.-There is no oxidized ore in the district, the surface having been deeply planed by glacial action in recent geologic time. The precious-metal content is about in the proportion of 85 of gold to 15? of silver by weight; hence, the silver is practically negligible. There are two classes of Porcupine ore, having very different characteristics; these will be referred to throughout this paper as Class A and Class B. Class A ore is a pure quartz with inclusions of schist. Generally it is heavily fractured .and breaks down readily to sharp, hard grains, about minus 10 plus 20 mesh, requiring further comminution to release the gold. It carries very little pyrite; the gold is entirely free and apt to be coarse, but often spongy, going into solution readily on that account. This gold is 60 per cent. to 85 per cent. free milling, depending on the grade of ore. Class B ore is an iron silicate schist, strongly laminated, carrying 4 to 5 per cent. pyrite; its specific gravity is 2.8 to 3.0, depending upon the amount of mineralization. In breaking the ore in the mine, generally over 25 per cent. of material through a ½ -in. ring is made; the ore readily breaks down in milling and makes a comparatively large amount of non-crystalline slime; owing to its high specific gravity, however, it is quick settling.' In my opinion, the gold in this ore is free, but so finely divided that it will neither pan nor amalgamate; it appears to be disseminated through the rock and not chiefly associated with the pyrite. Veins of Class A ore occur with or without side walls of Class B, and veins of Class B occur unassociated with Class A; more often the veins are closely banded, Class A and Class B alternating, generally with Class B in excess. Both classes of ore are more-or less blocky at times, and with ref¬erence to Class B this is indicative or low gold content.

Jan 3, 1915

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

GENTLEMAN: The year 1928 was another in the history of the Institute which was marked by quiet growth and steady progress. The total membership as of December 31, 1928, was 8703 as compared with 8438 on December 31, in 1927. Again the main increase has been in Members and the number of Junior Associates is less. As will be seen also by the Treasurer's report, the increase is reflected in larger receipts for dues indicating that fewer have had to be dropped for non-payment. There has been a gratifying increase in the number applying for reinstatement and it seems clear that interest in and attachment to the Institute has notably increased. The year was signalized by the merging of the Rocky Mountain Club with the Institute which brought to our roll one hundred and forty who were not previously members from among the men who have made the West. It also brought to the Institute a strong tradition of good fellowship and a fund of over $100,000, the interest from which is to be expended so far as may be, for purposes beneficial to the Western states. The Endowment Committee expects to see other and similar funds entrusted to the Institute and the Board has already appointed a special committee to consider all projects for expenditure of the revenue from them. It is felt that with the organization and personnel available in the Institute even modest revenues can be made to yield large returns in the way of scientific and technical knowledge. Within the year also, a third great Division has been organized within the Institute, building on the foundation of the old Iron and Steel Committee. The new Division signalized its independence by joining the Lake Superior Mining Institute in a visit to the Menominee Range in September and by furnishing material for a special volume of 353 pages, "Iron and Steel" Technology in 1928," printed and distributed in December. The Institute of Metals Division held its fall meeting with good attendance as one feature of National Metal Week at Philadelphia in October, and published its volume of Proceedings, running to 836 pages, in August. "Petroleum Development and Technology in 1927," 844 pages, came out in June and recorded the work of the Petroleum Division. A most interesting Fall meeting was also held by the Division at Tulsa,

Jan 1, 1929

By Noel Cunningham

Many excellent descriptions of the mills of the Porcupine district have been written, but no discussion exclusively devoted to the metallurgical technology has been given. These notes are intended to cover this feature briefly. They are based upon 21/2 years' mill operation in the district—i.e., practically since the beginning of metallurgical operations. Character of the Porcupine Ore.—There is no oxidized ore in the district, the surface having been deeply planed by glacial action in recent geologic time. The precious-metal content is about in the proportion of 85 of gold to 15 of silver by weight; hence, the silver is practically negligible. There are two classes of Porcupine ore, having very different characteristics; these will be referred to throughout this paper as Class A and Class B. Class A ore is a pure quartz with inclusions of schist. Generally it is heavily fractured and breaks down readily to sharp, hard grains, about minus 10 plus 20 mesh, requiring further comminution to release the gold. It carries very little pyrite; the gold is entirely free and apt to be coarse, but often spongy, going into solution readily on that account. This gold is 60 per cent. to 85 per cent. free milling, depending on the grade of ore. Class B ore is an iron silicate schist, strongly laminated, carrying 4 to 5 per cent. pyrite; its specific gravity is 2.8 to 3.0, depending upon the amount of mineralization. In breaking the ore in the mine, generally over 25 per cent. of material through a 1/2-in. ring is made; the ore readily breaks down in milling and makes a comparatively large amount of non-crystalline slime; owing to its high specific gravity, however, it is quick settling. In my opinion, the gold in this ore is free, but so finely divided that it will neither pan nor amalgamate; it appears to be disseminated through the rock and not chiefly associated with the pyrite. Veins of Class A ore occur with or without side walls of Class B, and veins of Class B occur unassociated with Class A; more often the veins are closely banded, Class A and Class B alternating, generally with Class B in excess. Both classes of ore are more or less blocky at times, and with reference to Class B this is indicative of low gold content.

Jan 1, 1915

By E. S. Machlin

The possibility that formation of voids under creep-rupture conditions may take place by the condensation of vacancies has been investigated theoretically. It has been concluded that nucleation of voids under creep-rupture conditions by vacancy condensation is highly improbable. However, growth of pre-existant voids by vacancy condensation is probable. A number of predictions made in this theory have been verified by the data. It has been predicted and checked that the product of rupture life and steady-state creep rate for preannealed metals and single phase alloys is an approximately invariant quantity, independent of stress, temperature, and atomic number for a given type structure. The direction of the effect of cold work on this product has been predicted and found in agreement with experiment. A number of experiments to evaluate the vacancy condensation mechanism further are described. SEVERAL papers have appeared recently which speculate on the origin of voids formed at grain boundaries under stress.' ' The object of this paper is to examine quantitatively the proposition that the voids produced in a creep test are a result of vacancy condensation. A result of this paper is a theory of creep-rupture. Void Nucleation Application of standard nucleation theory" to the problem of void nucleation leads to the following conclusions: 1—Homogeneous nucleation of voids requires a supersaturation ratio (concentration of vacancies in supersaturated to that in saturated solution) of 400 for a reasonable surface energy of 1000 erg per cm-and 1.4 for the improbably low surface energy of 10 erg per cm. 2—Heterogeneous nucleation of voids at plane interfaces between two phases requires a supersaturation ratio of 2.5 for a typical contact angle of 145 3-—Void nucleation about a solid particle may be accomplished at a supersaturation ratio of 1.17 for a typical value of work of adhesion? of 60 erg per The work of adhesion is the surface work 10 replace two solid-vauor surfaces by a solid-solid interface. enr ' between an oxide and a metal in the presence of a surface active element such as sulphur. Estimates of the supersaturation ratio at which voids are produced in diffusion experiments yield a maximum of 1.01. Inasmuch as the foregoing mechanisms of void nucleation probably will not operate at this level—too low a surface energy is required—the investigatol. is led to the conclusion that voids must already exist. That is, nucleation of voids probably does not occur. Rather, existing submicroscopic voids grow out to visible size. Already existing voids might be produced during solidification or working. Supercritical sized parlicles which contain cracks may act as heterogeneous void nuclei. Gas pockets may act as void nuclei. Experiments are desired to determine the nature of the heterogeneous void nuclei which grow out to voids in both diffusion and creep experiments. Void Growth Void growth might occur in at least two possible ways, depending upon whether the already existing void nuclei are at grain boundaries or within the grains. In the case of a spherical void far from a crystal boundary, vacancies are generated during creep as a consequence of the migration of suitable dislocation jogs' and are also annihilated at sinks. Under these conditions, a steady-state concentration of vacancies is built up in the crystal, defined by the condition that for any differential volume the rate of generation of vacancies in that volume equals the rate of annihilation of those vacancies." This equality would lead to the development of a gradient of vacancy concentration radially outward from the void surface up to a radius where the vacancy lifetime becomes equal for all directions of vacancy migration. The distance over which this vacancy concentration gradient extends equals about 2vD,T* where D, is the vacancy diffusivity and T:' the vacancy lifetime in a crystal outside the gradient in a zone of constant vacancy concentration. The vacancies generated in the region over which the gradient exists will annihilate more often at the void than elsewhere. Approximately a little over one-half the vacancies generated in the gradient zone will annihilate at the void. Hence, the growth rate of the void is given by on where R is the radius of void in centimeters, is the atomic volume, and R is the rate of generation of vacancies, number per centimeter" per second. R D and T* may be estimated in terms of other physical parameters." In particular, R = n.j e/b [3] where n is the average number of vacancy produc-

Jan 1, 1957

By E. L. Jr. Spain

This study was undertaken primarily to determine the reasons for certain varia-tions in the soundness of gravel aggregate taken from a number of widely separated points on the Tennessee River. Under laboratory tests, concrete made with these various aggregates it some cases exhibited marked differences in specific gravity, crushing strength and durability. Gravel was studied in detail from Chattanooga to the mouth of the river and to a lesser extent from Chattanooga to Knoxville. The causes of variation were determined, and variational curves were constructed, which accurately predict the composition of aggregate at any point on the river and therefore its relative suitability for use in concrete. The aggregate at any point is suited for making sound concrete; the variance of suitability is due to varying percentages of sandstone and weathered material, which are less sound than other constituents.

Jan 1, 1937

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By Willis H. Carrier

Particular interest in the ventilation of deep mines, especially those in South Africa, has been created by a very complete system of cooling of the world's deepest mine, the Turf shaft of the Robinson Deep in Johannesburg. The writer visited this mine in January, 1936, and again in 1937. During these visits and subsequently, a considerable part of the theory involved in rock cooling in tunnels was developed and this has been checked by practical observations of the rates of rock cooling made within mines. The purpose of this paper is to set forth the method of attack of the mine problem. The cooling or air conditioning of mines by the use of mechanical refrigeration was not wholly newl-5 when the Robinson Deep installation was made. The first mine to be cooled was the Morro Velho mine, in Brazil. The first installation in this mine was put into operation in December 1920, the refrigerant being ammonia.5 The surface cooling gave considerable benefit but it proved inadequate as greater depths were reached, therefore in 1929 two centrifugal refrigerating machines were installed at the 6000-ft. level. These were used in conjunction with the surface cooling system to furnish additional cooling at the lower levels. This later installation used Carrene as a refrigerant. This nonflammable refrigerant, having a boiling point of 104" at sea level, insured reasonable safety, since all parts of the machine operated at subatmospheric pressure. Very favorable reports have been received on the effectiveness of this installation, but no recent data are available. An interesting feature of that plant is that the condenser water is cooled by spraying it into the exhaust air from the mine at the base of the ventilation upcast, which permits the water to be cooled within a few degrees of the wet-bulb temperature of the air entering the upcast, and the only water that has to be supplied for condensing purposes is that lost by evaporation, or about 0.5 per cent of the volume circulating through the condenser. This plan affords an ideal means for the removal of the heat load from the refrigerating system, and of course also from the mine itself. In many mines, however, especially those in South Africa, there is no

Jan 1, 1940

By Willis H. Carrier

Particular interest in the ventilation of deep mines, especially those in South Africa, has been created by a very complete system of cooling of the world's deepest mine, the Turf shaft of the Robinson Deep in Johannesburg. The writer visited this mine in January, 1936, and again in 1937. During these visits and subsequently, a considerable part of the theory involved in rock cooling in tunnels was developed and this has been checked by practical observations of the rates of rock cooling made within mines. The purpose of this paper is to set forth the method of attack of the mine problem. The cooling or air conditioning of mines by the use of mechanical refrigeration was not wholly newl-5 when the Robinson Deep installation was made. The first mine to be cooled was the Morro Velho mine, in Brazil. The first installation in this mine was put into operation in December 1920, the refrigerant being ammonia.5 The surface cooling gave considerable benefit but it proved inadequate as greater depths were reached, therefore in 1929 two centrifugal refrigerating machines were installed at the 6000-ft. level. These were used in conjunction with the surface cooling system to furnish additional cooling at the lower levels. This later installation used Carrene as a refrigerant. This nonflammable refrigerant, having a boiling point of 104" at sea level, insured reasonable safety, since all parts of the machine operated at subatmospheric pressure. Very favorable reports have been received on the effectiveness of this installation, but no recent data are available. An interesting feature of that plant is that the condenser water is cooled by spraying it into the exhaust air from the mine at the base of the ventilation upcast, which permits the water to be cooled within a few degrees of the wet-bulb temperature of the air entering the upcast, and the only water that has to be supplied for condensing purposes is that lost by evaporation, or about 0.5 per cent of the volume circulating through the condenser. This plan affords an ideal means for the removal of the heat load from the refrigerating system, and of course also from the mine itself. In many mines, however, especially those in South Africa, there is no

Jan 1, 1940

By B. Tani, K. Anderson, I. Johnson, R. Schablaske

INVESTIGATION of the various rare earth-cadmium binary systems discloses the existence of a compound corresponding to the composition MCd6 in all systems save the La-Cd system. Lattice constants for all of the MCde compounds, except LaCd6 which apparently does not form, and PmCd6 whose synthesis was not attempted, are also recorded herein. Iandelli and Ferro 1 report the existence of the compound CeCd6. No additional information, structural details, and so forth are given. Elliott and Lemons2,3' have measured the vapor pressure of cadmium over CeCd6 and have calculated the activity of cadmium in solid CeCd6. These authors find that CeCd6 exists over a composition range from 5.967 to 6.098 (Cd:Ce ratio) at 584oC, and from 5.971 to 6.118 at 639°C. The following is an excerpt from the paper by Elliott and Lemons: 2 "Recently Mr. F. H. Ellinger of this laboratory has indexed an X-ray diffraction powder pattern of CeCd6.00 which we had prepared by gas phase reaction. The compound has a primitive cubic unit cell with a = 15.783 + 0.001A Based on the volume of the cubes surrounding an elemental cerium or an elemental cadmium atom, Mr. Ellinger finds room for 24.10 CeCd6 formula units in the CeCd6 unit cell; similar calculations based on CeCd2 and CeCd11 yield 24.18 formula units per unit cell. The presence of 24 CeCd6 units per unit cell seems probable with an X-ray density of 8.255 grams per cubic centimeter. The most one can say about in-terstitial~ is that there appears to be room in the crystal even at room temperature." Measurements of the solubility of the rare earths in liquid cadmium4 led to the discovery of GdCd6,

Jan 1, 1964