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By W. E. Keck, Paul Jasberg

The flotative properties of the principal minerals in Michigan's potential iron ores have been investigated to develop methods of bene-ficiation for the ores. One of these minerals, magnetite, is of considerable importance as a source of iron. Study of its flotation was similar to that of hematite1, another iron mineral in these potential ores. The present research consisted essentially of: (1) a survey of the literature on magnetite flotation, (2) the preparation of pure magnetite, (3) the development of laboratory procedure and (4) flotation experimentation. Literature on Magnetite Flotation.—For the purpose of this discussion, the results of previous work on the flotation of magnetite can be summarized as follows. The mineral has been floated with pine oil2, and it has also been separated from synthetic mixtures with silicates by the use of the same reagent2. Magnetite and apatite in iron-ore slimes have been separated by flotation of apatite with sodium palmitate3. These data were utilized in the present investigation. Preparation of Magnetite.—The pure mineral was prepared from the magnetic-separator concentrate of an iron ore (obtained from the Wither-bee Sherman Corporation, Port Henry, N. Y.). This concentrate was slowly comminuted with laboratory rolls and pulverizer to pass 65-mesh and was then tabled several times. Tabling yielded a relatively coarse magnetite concentrate, tailing and slimes. The two latter materials were rejected insofar as the present work is concerned, and treatment of the magnetite (table concentrate) was continued by separating it into — 65 + 200 and — 200-mesh sizes. Separation of the sizes was made by first dry screening and then wet screening. The —200-mesh material was rejected to eliminate possible introduction of error into flotation

Jan 1, 1939

By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3' for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.' An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962

By J. J. Arps

This paper reviews the methods currently in use for estimating primary oil reserves and discusses the principles on which these methods are based. Particular emphasis is placed on how these methods change with the type of information available during the life cycle of an oil property. This paper contains various novel estimating methods and shortcuts heretofore unpublished. INTRODUCTION Estimating oil reserves is one of the most important phases of the work of a petroleum engineer since the solutions to the problems he deals with usually depend on a comparison of the estimated cost in terms of dollars, with the anticipated result in terms of barrels of oil. His recommendations to management regarding the best course of action are therefore normally based on the most favorable balance between these two. Specific engineering problems which require such a knowledge of recoverable oil reserves and a projection of future rates are: [a.] the exploitation and development of an oil reservoir; [b.] the construction of gasoline plants, pipelines and refineries; [c.] the division of ownership in unitized projects; [d.] the price to be paid in case of a sale or purchase of an oil property, and the magnitude of the loan which it will support; [e.] the proper depreciation rate for the investment in oil properties; and [f.] evaluation of the results of an exploration program. This discussion will be confined to the various methods and tools which are currently in use for estimating oil reserves to be obtained during the primary phase of an oil-producing reservoir and for a projection of the future production rates. Reserves which may be obtained by secondary recovery methods or fluid injection programs and gas and gas condensate reserves will not be discussed in this paper. Unfortunately, reliable oil reserve figures are most urgently needed during the early stages when only a minimum amount of information is available. Management's interest in the oil recovery from a property—aside from its use for accounting purposes—usually declines when the property approaches its economic limit, just at the time when the reliability of the estimates is at its best. To illustrate this general idea a chart is presented (Fig. 1) showing the three periods in the life of an imaginary oil property. Time is shown on the horizontal axis, while the cumulative production and estimated ultimate recovery are plotted vertically. No particular units are used and this schematical chart is not to scale. During the first period, before any wells are drilled on a property, any estimates will of necessity be of a very general nature, based on experience from similar pools or wells in the same area, and usually expressed in barrels per acre. This will

Jan 1, 1957

By G. M. Ikeda, J. G. Sibakin

An investigation was carried out to determine the variables affecting the coiling temperature of strip in the 56-in. hot strip mill. After statistical treatment, equations have been derived to determine the temperature drop between mill and coiler for both full spray (top and bottom) and top spray only practices. The individual influences of each variable in the temperature drop were derived for both practices. Limitations of the present practices were shown and adjustments in cooling for increased rolling speeds were suggested. A method of estimating the required number of sprays, their spacing, pressure, etc., to achieve a desired temperature drop is developed. MAXIMUM finishing temperature of a hot strip mill is mainly determined by the rolling speed, gage, and the temperature of the bar entering the mill. This finishing temperature may be limited by the maximum admissible coiling temperature in cases when either the cooling facilities on the runout table are not adequate or, more generally, when the cooling capacity of the runout table and the production capacity of the continuous mill are out of balance. Some time ago, the balance between these two factors was not considered detrimental to production. Recently, a new drafting schedule was introduced which increased the production rate, the entry temperature, and hence the finishing temperature. Thus, the restriction of the maximum specified coiling temperature became an important factor for many of the thicker gages. An investigation of the factors determining the coiling temperature may be, therefore, of considerable importance. A brief description of the available equipment will be a useful illustration of the techniques and methods used for this investigation. The 56 in. continuous hot strip mill is composed of six 4-high stands each containing two 221/2-in. diam work rolls and two 45-in. diam back-up rolls. Either of the last two stands can be used as the finishing stand. Which stand is used is dependent on the total percentage of reduction to be taken over the whole train, i.e., on the entry thickness and the final gage. The characteristics of these last two stands are given in Table I. Table I. Operational Characteristics of Nos. 5 and 6 Stands No. .5 NO. 6 Maximum voltage GOO 600 Power, hp 30(10 W00 I normal, kilonmp 4.35 3.73 Rpm of motor and rolls ISO 15 0 ITS to 300 Spettl ot strip, fpm 333 6 to 376T.2 103) to 2062 The speed of the finishing stand varies with the amount of reduction, strip width, and the exit gage. Finishing speeds in general use for varying gages are shown in Table 11. These speeds may change with an increase or decrease in the entry temperature of the strip. Even though the maximum speed of No. 6 stand is shown as 2062 fpm, this has so far never been attained,

Jan 1, 1957

By D. C. Buffum, L. D. Jaffee

THAT the path of brittle fracture in temper brit-tle steel differs from the path in unembrittled steel has been known for some years1 More recently it has been recognized that alloy steels, at least, display two forms of temper brittleness1 which may be called upper-nose and lower-nose. No experimental evidence has been published, however, to show that the two forms can be distinguished by simple inspection of brittle fractures. Fig. 1 is a photograph of the fractured surface of a V-notch Charpy specimen of SAE 3140 steel in which temper brittleness developed during heat treatment in the lower-nose temperature range.' The steel was austenitized 1 hr at 900°, tempered 1 hr at 675", and embrittled 48 hr at 500°C, with water-quenching after each treatment. The temperature of transition from ductile to brittle fracture in the Charpy test was + 2°C (criterion of transition: 100 pet fibrous). The hardness was Re 25; the austenite grain size ASTM 8. This specimen was broken at 150°C in the standard Charpy test and absorbed 6.6 ft-lb; its fracture was rated 0 pet fibrous. Fig. 1 shows that the fracture appeared rough to the naked eye. At the side of the specimen away from the notch (the side which was in compression during the test), the surface as a whole deviated sharply from a plane. At higher magnification, X60, the surface gave

Jan 1, 1959

By M. T. Hepworth, R. Schuhmann

Hydrogen solubility measurements were made on a series of Ti-O alloys, and a portion of the 800°C isotherm for the Ti-O-H system was determined. Activities of oxygen and titanium were calculated from the experimentally measured activities of hydrogen, using ternary Gibbs-Duhem integrations. The data were extrapolated to obtain thermo-dynamic properties of binary Ti-O solutions. The thermodynamic properties of a Ti-0 solid solutions thus determined were compared with properties predicted from interstitial models. The Gibbs-Duhem equation, long used to calculate activities in binary systems, has been extended. recently to ternary systems.1"3 When the activity of one component in a ternary system is known as a function of composition, the activities of the other two components can be calculated from that of the first by an integration procedure, provided certain restrictions are observed on the path of integration. Often the activity of one component in a ternary system can be measured readily, while the activities of the other two components are difficult to measure. Gibbs-Duhem calculations are especially applicable to such systems. The further possibility arises of developing a new and indirect approach to activity measurement in binary systems. The proposed new method for binary systems consists of adding varying amounts of a third component whose thermodynamic behavior is easily measured. The activity of this added component is determined experimentally as a function of composition. Then the activities of the two components of the original binary system are calculated by Gibbs-Duhem integrations and extrapolations. For the work to be described in this paper, the Ti-0-H system was selected as a promising system for evaluating this approach. Investigations of the Ti-H system have shown that the activity of hydrogen can be measured precisely with little difficulty. Pure titanium transforms from a low-temperature a form (hcp) to a higher-temperature /3 firm (bcc) at 882.5"~ The phase transformation occurs in a temperature range where hydrogen pressures are easily measured. Also, the diffusivity of hydrogen at temperatures above 600" or 700"~ is large enough that equilibrium can be reached within a reasonable time.

Jan 1, 1962

By E. W. Davis

THIS nation has been depending upon the Lake Superior iron ranges for most of its iron ore requirements for over half a century. Furthermore, it can continue to draw the major portion of its ore requirements from the same source for another century or more, but to accomplish this, great changes must take place in the present ore mining industry. Preliminary preparations for these changes are now underway and in the next few years decisions of far-reaching importance must be made. But to understand the situation, it is first necessary to know something of the nature and occurrence of the Lake Superior iron formation. So far as is known, the merchantable grades of iron ore remaining in the various Lake Superior ranges are as shown in Table 1, which shows that

Jan 1, 1947

By Nathaniel Hen

IN the United States, in the 2 1/2 years since the rescinding of the wartime order closing gold mines, conditions have not yet returned to normal. Shortages of man power have prevented some mines from operating at all, and most of those in operation are still at reduced capacity. This fact, combined with shortages of materials, the high cost of supplies and labor, high tax rates, and a fixed price for the product have made the past years rather rough ones for gold producers. In foreign countries conditions are rather similar. In Canada several new mines are coming into production and some others are enlarging. Costs have not increased as much as in the United States and gold production is being encouraged. Recently a bonus of 20 per cent on increased production has been proposed. In South Africa, where gold mining is of major importance in the national economy the industry is also in a favored position with government; new discoveries of major importance there will markedly increase the gold output. Demand for labor is rap-

Jan 1, 1948

By R. K. Waring, E. C. Truesdale

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By E. C. Truesdale, R. K. Waring

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By M. H. Richman, E. S. Meieran

An analytical method is presented which enables the electron diffraction patterns from a twinned region to be indexed. The method has only been applied to (112) twins in bcc lattices, but can easily be adapted to other types of twinned lattices. Calculations of all twin spots, including those superimposed on matrix spots, is made possible by this method. SINCE the advent of transmission electron microscopy, the analysis of selected-area electron diffraction patterns has become very important in the interpretation of electron micrographs. Frequently, as in the case of some martensites, twinned areas are observed and give rise to complex diffraction patterns, which so far can be analyzed only for the simplest orientations of the thin foil specimen with respect to the electron beam. In order to simplify the analysis of twin patterns of more complex orientations, an analytical method was devised which is capable of predicting the positions of all reflections from both matrix and twin regions for all possible foil orientations. Although the method has only been applied to the case of bcc metals twinned about a (112) plane, it is equally applicable to other Bravais lattices. This method has been successfully applied to selected-area electron diffraction patterns of Fe-Ni and Fe-Ni-C martensites and drawn tungsten wire. PROCEDURE Imagine the reciprocal lattice corresponding to a bcc material, with each point hkl representing the crystallographic plane (hkl). Since the extinction conditions require that for this lattice, only reflections where h + k + 1 = even integer are allowed, the three dimensional reciprocal lattice is actually fcc. Since in real space twinned regions and matrix regions are mirrored across a (112) plane, the twinned reciprocal lattice is derived from the matrix reciprocal lattice by a rotation of 180 deg about a (112) direction. While it is possible to calculate how a point hkl will shift under a twinning transformation to a new point htktlt using only the reciprocal lattice based on the orthonormal vectors [100], [010], and [001], the calculations are greatly simplified if a new orthonormal coordinate system containing the twin axis is introduced. The twinning operation then becomes a simple rotation of 180 deg about a principal coordinate axis (in this case the twinning axis), and a retransformation back to the original reciprocal space will give the position htktIt of the twinned reflection.

Jan 1, 1963

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By D. I. Bardos

The occurrence of Laves phases (AB,) in various binary alloy systems has been reviewed in recent papers.13 Iron forms Laves phases with Sc-, Ti-, V- and Cr-group elements. However, two of the corresponding Laves phases with cobalt, namely MoCo, and WCo,, are missing. Nickel forms binary Laves phases with Sc and Y, but not with any Ti-, V-, or Cr-group element. These conditions are schematically illustrated in Table I. That electron concentration is a significant factor in determining which type of Laves phase is formed in a given case was recognized long ago by Laves and Witte,4 This concept has been more recently applied to Laves phases formed by transition ele-ments. It now appears that the average electron concentration (average number of electrons per atom outside of the closed shells of the component atoms) may be an important factor also in determining whether or not a Laves phase can occur at all in a given system. As shown in Table I, in the transition element systems considered Laves phases are absent at electron concentrations of 8, or larger (to the right and below the double line in Table I). These absences clearly cannot be accounted for on atomic size considerations, as evidenced by the many inconsistencies apparent in Table 11. While the ideal radius ratio for Laves phases is 1.222, in the systems which do have Laves phases the ratios of CN 12 radii range from 1.10 to 1.46. The consistent absence of Laves phases at RA/RB< 1.10 might be attributed to the low values of these radius ratios. However, Table II shows that absences also occur irregularly throughout the radius ratio range covered. In a previous paper7 it was concluded that, in transition element systems forming u-phases, silicon may act as an acceptor of electrons, thus stabilizing the u-phase at electron concentrations higher than

Jan 1, 1962

By H. Gisser

Recent experimental work has demonstrated (1)2 that ammonia and oxides of nitrogen are formed during the aging of smokeless powder. This is significant in connection with the problem of "season cracking," or stress corrosion of brass cartridge cases in view of other work(1) indicating that stressed and "stress- relieved" cases stored with small quantities of added ammonium nitrate crack on firing. The deterioration of stressed brass by ammonia has been known for some time(z) and it appears therefore that stress- corrosion cracking of brass cartridge cases is intimately associated with the so-called "powder volatiles," ammonia and oxides of nitrogen, both of which are decomposition products of smokeless powder. Working on the hypothesis that any barrier which prevents the powder volatiles from reaching the brass surface will reduce the incidence of stress-corrosion cracking, it was considered desirable to investigate the use of organic resin films to accomplish this purpose. The possibility of formation of ammonia within the nitrocellulose powder charge and by reduction of nitrogen oxides on the surface of the brass case requires that the barrier film be resistant both to ammonia and oxides of nitrogen. The film must also be impermeable to ammonium salts, either solid or in solution, since these salts and water necessarily appear within the powder charge. The usefulness of the

Jan 1, 1945

By E. C. Truesdale, R. K. Waring

THE Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO + CO = Zn + CO2[I] C + CO2 = 2CO[2]. Each of these reactions is dependent upon the other for the supply of CO and C02, respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2O[3] C+ H2O=CO+H2[4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between 1100° and 1300°C the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier&apos;s statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented.*

Jan 1, 1941

By M. Dayne Aldridge

A discussion of the definition of automation in mine ventilation applications is presented. The results of theoretical studies, experiments, and practical experience from work in the United Kingdom, Belgium, Poland, the Soviet Union, and the United States are summarized Conclusions are drawn from these efforts and the prospects for the future development of automatic mine ventilation systems are explored.

Jan 1, 1980

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By John B. Baker, Bernard B. Betty, H. F. Moore

Fox several years there has been in progress in the Materials Testing Laboratory of the University of Illinois an investigation of creep and fracture of lead and lead alloys. In the course of this investigation it has been shown that the phenomenon of creep occurs in part at the grain boundaries of lead and lead alloys. To study the occurrence of creep and the development of fracture within crystalline grains, two series of tests of single crystals of lead have been carried out. The first of these, a preliminary series, by Mr. Betty, has been described.1,2 The second, pursued by Mr. Baker for his doctoral dissertation, was carried out under the direction of Professor Moore, with the assistance of Prof. G. L. Clark in the X-ray work, and the cooperation and advice of Mr. Betty. This paper is based on the test data obtained in this second series. Single crystals of a very pure commercial lead have been prepared, some of them tested to measure creep, others tested to fracture under long-continued steady load, and still others tested under cycles of repeated tension. An interpretation of the test data of these single-crystal tests is offered, which is a combination of parts of several well-known theories. SPECIMENS The single-crystal specimens were made from a piece of very pure commercial lead sheathing. A spectroscopic analysis of one of the single crystals showed the presence of 0.005 per cent Bi, 0.0001 per cent Cu and 0.0003 per cent Ag. Preparation.-The Bridgman method of casting single-crystal speci¬mens was used.3 The specimens were cast to the shape and size shown in Fig. I (dimensions in Fig. 4c) in a duralumin mold. Molten lead does not stick to duralumin. Fig. 1 shows the mold and the blast flames for heating. After the mold had been heated to the temperature of molten

Jan 1, 1938

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955

By W. D. Robertson, E. G. Grenier, V. F. Nole

The electrical, mechanical, and corrosion cracking properties of an age-hardenable Cu-Ni-Si alloy have been studied over a range of time, temperature, and deformation states for the purpose of determining the relationship between the properties and the structural state. The precifitate has been identi3ed as and the sites of preferred precipitation have been located by electron microscope studies of the structures developed by various combinations of heat treatment and plastic deformation. An extreme form of deformation banding has been observed in the aged alloy that results in high strain concentration in bands lying parallel to {111} planes. These bands are the structural paths along which transcrys-talline cracks propagate in the deformed alloy. The observations provide a basis for a general mechanism of transgranu-lar corrosion cracking of face-centered cubic alloys in terms of stacking fault probability. AMONG the age-hardening copper alloys the copper-nickel-silicon (Silnic Bronze) type is outstanding in exhibiting a high strength combined with a considerable capacity for cold working, a relatively high conductivity, and a low to negligible susceptibility to stress corrosion cracking. It is not a new alloy and it has been the subject of a number of investigations,1-5 which were made primarily to establish practical composition and heat treatment limits. The structural characteristics of the aging processes in this alloy have not previously been studied in detail. This particular investigation was undertaken to explore, in detail, and over a wide range of conditions, the properties obtainable by various combinations of working and heat treatment and to correlate structural changes with the observed mechanical, electrical and corrosion properties. MATERIAL AND PROCESSING Eight different commercial heats of the alloy were made and used in the investigation. The range of composition among the eight heats is shown in Table I. Billets, 8 by 24 in., were cast into water-cooled molds, extruded to 1.687-in. rod, and quenched in water after extrusion. Extruded material was rod rolled to 0.750 in., annealed at 1450° F for 2.5 hr, and quenched in water. Subsequent working operations were performed by tandem rolling to various sizes depending on the degree of reduction required. Final cold-working operations were performed by drawing to a uniform size of 0.187 in. diam and straightening by a roller straightening machine (Lewis). The combinations of heat treatment, working and aging that were investigated are summarized in Table 11; the various treatments were performed in the order given in each row of the table, and they will be subsequently identified by the symbols shown in the first column. SOLUTION TREATMENT All material investigated in the cold-worked condition, or cold worked prior to aging, was solution

Jan 1, 1962