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By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By J. H. Swisher

HIGH-temperature anneals in wet hydrogen are widely used in research as a technique for decarburiz-ing Fe-C alloys. This technique is also used commercially in processing low-carbon steels for magnetic applications. The results of some calculations to be presented show that for temperatures up to 1100°C there is a critical temperature for maximizing the decarburization rate of alloys containing about 0.1 pct C. The low-temperature portion of the iron side of the Fe-C phase diagram1 is reproduced in Fig. 1. Preliminary calculations show that the critical temperature is between 727" and 905°C. In this range, the alloy contains two phases during heat treatment, ferrite and austenite. Decarburization therefore occurs by a process termed "diffusion accompanied by a phase change".' For intermediate stages of decarburization, the carbon concentration profile in a flat plate is shown in Fig. 2. The carbon content increases linearly from zero at the surface to a value, cB , at the two-phase boundary. cB is known from the phase diagram, see Fig. 1. At the interface where x = 5, the carbon content increases to ci, the initial concentration in the alloy. smith3 has derived an equation which describes the rate of movement of the boundary. With a rearrange-

Jan 1, 1969

Richard Moldenke, New Pork, N. P. (communication to the Secretary*):—Iu following the discussion of the specifications for cast-iron and finished castings, I mas strongly impressed with two points which might be ventilated to advantage more fully from the view of the practical foundry-man. First, the reasons why only silicon and sulphur were specified and not phosphorus, manganese and carbon; and second, why but little was said concerning the presence of iron oxide in the material.

Jan 1, 1905

By R. J. Reynik

A semiempirial small flunctation theory of diff- sion in liquids is presented, which employs a fluctuation energy assumed quadratic for a small atomic or molecular displacement and Einstein's random-iralh model. The resulting diffusion equation is given by In these equations. D is the diffusivity, is the average liquid shite coordination number (at interatomic distance d. cm. T is the absolute temperature, xu. em, is (the diffusive displacement. K, is the quadratic fluctuation energy force constant, and rg, cm, are the radii oj diffusing atoms A and B, respectively. The quantities Xn and K are calculated from the computer-filled values of the slope and intercept. respectively. The radius of self-diffusing atom or radii and of diffusing atoms A and B are eta United and compared with values reported in the literature.. The predicted linear variation of diffusivity with. It tempera lure htm been observed in approximately thirty-iire metallic liquid systems, and in over seventy-fiee other liquid systems, including the organic .alcohols, liquified inert gases, and the molten salts, ALTHOUGH the average density within a macroscopic volume element of liquid is constant for fixed total number of atoms. pressure. and temperature, there exist microscopic: density fluctuations within the respective volume element. As such the microscopic volume available to an atom and its Z first nearest neighbors at any instant of time fluctuates above and below the average volume available to these atoms. If one assumes that liquid state atoms vibrate as in a solid. and further postulates that the mean position of any atom in the liquid state is not stationary. but shifts during every .vibration a distance 0 5 j 5 xo. then every atom in the liquid state continuously undergoes diffusive displacements which vary in the range 0 5 j 5 ro. Mathematically. for a binary liquid system consisting of atcrms A and B. the maximum diffusive displacement. .YO, is defined by the equation: where d is the average liquid state interatomic distance at specified liquid state coordination number Z. and v~ \ and vg are the effective radii of diffusing atoms A and B: respectively. For self-diffusion. r^ equals rg , and Eq. [I.] reduces to: It is interesting to note that Eq. [l] or [2] can be used to compute the radii of the diffusing atoms, provided one had an experimental evaluation of xo. As such. the computed radii could be compared with metallic or crystallographic ionic radii to ascerlain the electronic character of the diffusing atoms. Thus it is proposed that in the liquid state the n~otion of an atom relative to its original equilibrium position of oscillation represents the thermal vibration of any atom and its Z first nearest neighbors. while the small and variable displacements. 0 5 1 5 xc,. of the centers of oscillation represent the complex diffusive motions of the atoms at constant temperature and pressure. This is consistent with data obtained from slow neutron scattering by liquids1 ' and resembles an itinerant oscillator model of the liquid state.'" It is further postulated that the atomic displacements characterizing the liquid state diffusion process are essentially a random-walk process. As such. it nlay be described by Einstein's equation:' where D is the diffusivity. sq cm sec-'. j2 is the mean square value of the diffusive displacement. and i> is the frequency of density fluctuations giving rise to diffusion. FORMULATION OF DIFFUSION EQUATION The effective spherical volume occupied by an atom, as a consequence of a microscopic density fluctuation which enlarges the volume available to any atom, exceeds its average liquid state atomic volume by an amount: where AV is the enlarged spherical volume, v is the radius of the diffusing atom. and j is the elementary displacement distance from the original center of oscillation of the vibrating atom to a new center of oscillation position. For small atomic displacements. where c is a constant whose value depends upon the assumed geometry of the enlarged volume. For a spherical increase in volume, c equals 4nr2. Following the treatment of Furthl' and ~walin." assuming the enlarged volu~nes AL7 for the diffusing atoms are distributed in a continuunl. the probability of finding a fluctuation in the size range 0 5 j 5 xo defined by Where c includes the geometric constant cl and Eij) is the fluctuation energy causing the volume change. But the proposed model assumes all the Z first nearest-neighbor atoms are centers of oscillation. and hence the probability that any of these atoms is adjacent to a fluctuation of magnitude 05j5xo is unity. Thus:

Jan 1, 1970

Jan 1, 1879

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

R.. B. T. KILIANI, New York, N. Y.-I do not care to discuss Mr. Taggart's paper in the light of theory, as that has been very well done by Prof. Bell,1 but I should like to criticize some of his conclusions, in the light of actual operating practice at plants all over the country. 1. Mr. Taggart's first conclusion is that in crushing average ore, the character of the gangue has little effect on the efficiency of the mill. This, I believe, is not in accordance with the usual practice, since in crushing a hard ore the capacity will be much reduced below what it would be with a softer ore, while the power consumed will be practically independent of the character of the ore, being proportional only, to the load of ore and balls in the mill. 2. Mr. Taggart's second criticism is that the Hardinge mill is not suitable for grinding soft, tough material. In answer to this I might mention that the mill is being used for grinding tough, dnctile material, such as metallic aluminum, and also for grinding licorice root. 3. He says that the ball-mill works more efficiently on material of intermediate size, say 1/2 to 3/4 in., than on either coarser or finer feed.. This is true as to coarser feed. For the most efficient work, I believe that a ball-mill should be fed with material not coarser than 1 1/2 in.; it' will handle material up to 3 and even 4 in., but the reduction from 3 or 4 in. to 1 1/2 in. can be done much more cheaply and efficiently by rolls or disk crushers than in the ball-mill. 4. As to Mr. Taggart's fourth conclusion, that a greater ratio of reduction can be expected with feed of an intermediate size than with a coarse feed, I have not enough information to express an opinion. 5. His next conclusion is that steel balls are much more efficient crushing media than pebbles. Steel balls are undoubtedly more efficient for crushing coarse feed. On fine material they are also more efficient as to tons per horsepower crushed to 10-mesh, but on fine material I think it will be found that flint pebbles are cheaper than cast-iron balls, per ton of ore, although there will be a saving in power per ton by using cast iron instead of flint. The increased cost of crushing with cast iron will be due to the higher cost of iron at the present time. 6. Mr. Taggart's sixth conclusion coincides with present practice, that steel balls will grind as fine or finer than pebbles when working on the same feed.

Jan 1, 1918

By John M. Lovejoy

FEDERAL regulation of the petroleum resources of the nation has long been an interesting topic for discussion. A plan to accomplish Federal control has now taken definite form. At the request of the President of the United States, a bill to be known as the Petroleum Conservation Act of 1939 has been presented to Congress-H. R. 7372, offered by Representative Wm. P. Cole, Jr., and more usually known as the Cole bill. It is an act ostensibly designed to conserve our petroleum resources, through regulation of production practices. Hearings are being held currently by a subcommittee of the Interstate and Foreign Commerce Committee, in compliance with the request of the President to report the bill early in the next session of Congress.

Jan 1, 1939

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By H. D. Merchant

NUMEROUS publications have examined hot hardness of metals and alloys. Some have studied creep in long-time hardness tests, few of which, however, were tested under a spherical indentor. 1-3 The results of Mulhearn and Tabor' indicate a parabolic-type creep for indium and lead, whereas Moore and Tabor2 how a logarithmic-type creep for indium. Similar semilog relationships between hardness and time have been found by Goffard and wheeler3 for magnesium, aluminum, and their alloys. In this note, the elevated-temperature hardness of some complex alloys, shown in Table I, was examined to discover whether any basic information about the deformation behavior of the alloys could be obtained. One of the alloys, H-13 alloy steel, was tested for short-time creep tests to examine the hardness-time relationship at various temperatures. A standard Brinell Hardness Tester, mounted with an appropriate furnace and 99 pct A12O3 poly-crystalline indentor, was employed for the purpose. The alloys were tested at temperatures from room to 1400°F for 30 sec under 1500-kg load. The creep studies were conducted for about 8500 sec at 7l°, 500°, 1000°, and 1200°F. For constants A and B, a relationship of the type H = Aexp(-BT) [ll was obtained for all alloys between hardness, H, and temperature, T. In the semilogarithmic plot, the data points for each alloy were arranged into two groups, each group on a straight line with a specific set of A and B values. These results are in agreement with many such observations on hot hardness, notably those of Westbrook for pure metals,4 The thermal softening coefficient, B, and transition temperature, Tt, for various alloys are shown in Table I. The change in slope around the transition temperature suggests an apparent change in the mechanism of deformation, probably from the shear (below Tt) to the diffusion type of mechanism. At the temperatures above Tt, for constants A' and B, a relationship of the type was obtained between H and T, Fig. 1. The nature of the equation, where R is gas constant, suggests the possibility of a thermally activated mechanism of deformation above Tt. The constant B' may hence be defined as the apparent activation energy of indentation. The B' values of various alloys are shown in Table I. A plot of B vs B' gives a curvilinear relation shown in Fig. 2. The indentation-creep data for H-13 alloy steel is shown in Fig. 3. At 71" and 500°F, the creep initially follows the logarithmic time law. However, the indentation size stabilizes after 7 sec at 71°F, and after 10 sec at 500°F. Further increase in loading time has no effect on indentation size. The creep of 1000° and 1200°F follows the logarithmic time law for the first 1000 sec, after which the

Jan 1, 1964

THE members arrived at Ticonderoga, N. Y., at noon, Tuesday, October 15th, and were received by Mr. Cyrus Butler, Chairman of the Local Committee of Arrangements. During the afternoon the works of the American Graphite Company and the Horicon Iron Company were visited under the guidance of Mr. Butler, President of both companies, and of Mr. William Hooper, Superintendent. An excursion was then made, in carriages, to old Fort Ticonderoga, on Lake Champlain, after which the party were driven to the Rogers Rock Hotel, on Lake George. The first session of the Institute was held in the parlor of time hotel on Tuesday evening. Mr. Eckley B. Coxe, President of the Institute, opened the proceedings with the following address: I shall ask your attention, this evening, to a few reflections upon the subject of mining engineering as a profession in the United States, its past, its present, and its future, and its duties and oppor¬tunities with reference to the proper development of our great min¬eral resources. Thirty years ago, there were scarcely any mining engineers in this country, and but few in England, and there were no institutions where young men could be educated for the profession in the Eng¬lish language. France and Germany have been able for about a century to boast of mining schools of a high character, that number among their graduates such men as Humboldt, Weisbach, Rittinger, Combes, and Gruner. Of the few we then had worthy of the name of "mining engi¬neer," some had studied in the continental academies, and others were graduates in the school of practical experience, and had learned their profession in mines and smelting-works. Their work con¬sisted principally in making surveys and maps of mines and mining properties, geological reports, and analyses of ores ; but the mining engineer whom we often meet with now, who has studied chemistry, physics, mineralogy, geology, mechanics, and drawing; who is more or less familiar with machinery and its construction, and with the practical management of mines or smelting-works, and who is an expert in some one branch of his profession, would have been very difficult if not impossible to find in the United States. The induce¬ments held out to ambitious and talented young men to enter the

Jan 1, 1879

By NEWTON B. KNOX

THE war has forced the principal industrial nations of the' world into the strait jacket of a closely controlled economy; taxes have been heaped upon all enterprises in order to maintain the armed forces and to deprive the people of the ability to bid for goods now unavailable. These restrictions, controls, and taxes are unlikely to disappear entirely after the war has been won, for debts will remain to be paid with a long period of difficult readjustment. Although the new economy will doubtless offer plentiful opportunities for the advantageous use of capital, no investor can ignore the favorable conditions offered by industry in Latin America, where taxes are relatively low and the restrictions on free enterprise comparatively mild. In mining in South America, the great international corporations have

Jan 1, 1944

By A. S. Nowick, E. S. Machlin

ONE of the main criteria used to rate the heat-resisting properties of alloys is stress rupture.1 During a stress-rupture test a tensile specimen is held under a constant load at a constant temperature until it fractures. The chief measurement made during this test is the time required for rupture at the specific test stress and temperature. It was found empirically from a series of stress-rupture tests at a constant temperature that when the logarithm of the time for rupture is plotted against the logarithm of stress a straight line is obtained within experimental error.2~3 This method of showing stress-rupture data has been adopted by many investigators and the KACA.4 By interpolation and extrapolation from these plots, values of the stresses required to rupture the specimens (the rupture strengths) in 10, 100, and 1000 hr are obtained for specific temperatures. Alloys are then rated for a particular application on the basis of their rupture strengths at the rupture life that most nearly represents the application. Inasmuch as stress rupture is an important criterion in rating heat-resisting alloys, it would be advantageous to know the quantitative dependence of the time for rupture on stress, temperature, com- position, and structure. In order to obtain this information, an investigation was made at the KACA Cleveland laboratory during the spring of 1945. The theory of rate processes was used because it has been found to apply to certain processes such as chemical reactions, viscous flow, and creep that occur at a definite rate for given conditions. It was thought that stress rupture was such a process. An equation was derived that gives, for a given com- position and structure, the dependence of the time for rupture on stress and temperature. The investigation is part of a general program to provide information that will lead ultimately to the development of better alloys in order that the efficiency and power output of gas turbines used in aircraft propulsion can be increased. THEORY The theory of rate processes will first be discussed as a general theory. It will then be shown that if stress rupture of heat-resisting alloys can be treated as a rate process, certain equations must be satisfied. Later sections will then show that these equations are satisfied. General Theory of Rate Processes The theory of rate processes5 eveloped by Eyring and others has been applied to chemical reactions as well as to other processes such as viscosity of liquids and diffusion. In every case in which rate- process theory can be applied, there is a small subdivision, so that the macroscopic process is the net effect of all the small processes. This smallest subdivision is called the "unit process.'' For example, in a chemical reaction the unit process is

Jan 1, 1947

By John Wulff, J. H. Hollomon

SERVICE failures in brass condenser tubes are often due to corrosion. One of the commonest types of corrosion reveals a surface structure of redeposited copper.1 The study of the effect of alloy addition agents in preventing this kind of corrosion has received impetus from the extensive publication of Bengough and May.2 The mechanism of such inhibition gauged from immersion corrosion,' cell corrosion,' and electrolytic potential' measurements is controversial. This controversy may be attributed in part to a lack of definite knowledge5 of the actual nature of the initial films formed in corrosion experiments. In our own corrosion work on copper and 70-30 brass this lack became apparent and necessitated an examination of surface films by X-ray and electron diffraction methods. The present paper is but an introduction to the subject of inhibition and reports the structure of films formed in active corrodents. EXPERIMENTAL PROCEDURE The arsenical coppers and brasses used in this investigation were made by one of the writers* in the plant of the Revere Copper and Brass Co. at Rome, N. Y. Standard commercial melting practice was followed. O.F.H.C. copper and electrolytic zinc were used and all arsenic additions were made by additions of a master copper alloy. The final analyses are given in Table I. Likewise, the extrusion, cold-rolling, and intermediate anneals employed followed standard usage. Final heat-treatments were given to all materials to produce a similar grain size (0.035 to 0.045 mm. for brass and 0.015 to 0.025 for [ ] copper) for the alloys containing various percentages of arsenic. Samples ¼ by ½ by ¼ in. were cut from sheet material resurfaced and finished with 0000 metallographic papers. The surfaces were all degreased in alcohol and benzine before immersion. After immersion in the corrodent, they were washed gently in tap water, dipped first in alcohol and then in pure benzine and allowed to dry in the diffraction apparatus. The reflection electron diffraction apparatus used has been described by Burwell

Jan 1, 1941

By A. F. Andresen

IN the course of another investigation the lattice parameters were determined for a series of compositions of tin in copper. Ten-gram samples of the alloys were made from spectroscopically pure tin and copper. The metals were weighed and placed in graphite capsules (previously fired at 5500°F) which were then sealed individually in evacuated vycor tubes. The tubes were mounted on a spit, transverse to its axis, which continually rotated the melts in a furnace. After homogenizing, filings were made of one third of each slug by filing off a complete cross section. A 325-mesh sieve was used to obtain the powder for the X-ray determination. The sieved powders were annealed in vacuo at 600°C for 24 hr to remove the cold work, and then quenched. The lattice parameters were determined with a flat-plate back-reflection camera using CuKa radiation (A., = 1.5405A, A,? = - 1.5443A). With this radiation the (331) and (420) reflections appeared close to the focusing region. As reference lines were used the same reflections from pure copper powder, between which the (420) lines of all these alloys are situated. The variation of the systematic error over this angular range was found to be less than the estimated experimental error ±0.0005A which is indicated in Fig. 1 for all but the sample with 8 pct Sn. As a check some of the powders also were examined in a regular Debye-Scherrer camera with the Straumanis film mounting. The parameters were here evaluated by extrapolation against cos2? to ?= 90o. The results are shown in Fig. 1 where the lattice parameters in Angstrom units are plotted as a function of weight percent of tin. The reflection lines for the 8 pct alloy were not clear at first, perhaps due to coring. Several measurements were made after different annealing programs on two separate

Jan 1, 1959

By J. D. Clark

ONE'S lifetime does not usually offer the oppor-tunity to observe and be a part of the commercial development of an entirely new material. Petalite has been known for over a century, but at first it was presumed rare. However, it was found to be so abundant that it has become a new and extremely useful industrial tool. Mineralogy Petalite is a lithium-aluminum-silicate mineral. It was from petalite that J. A. Arfwedson first discovered lithium in 1818. The theoretical composition of Li2O • A12O8 • 8SiO2 is equivalent to 78.4 pct silica, 16.7 pct alumina and 4.9 pct lithia. The mineral in its known commercial occurrence is colorless to white and rarely gray, transluscent and rarely transparent. It is brittle, has a vitreous luster, and occurs usually in cleavable masses (fig. 1). It is classified as a di-silicate, but is similar in composition to the metasilicate spodumene, Li2O.-Al2O8-4SiO2 (table I). However, their specific gravities are quite different (3.13 to 3.20 for spodumene, 2.39 to 2.46 for petalite). Occurrence Petalite specimens have been reported in many localities; however, there are only three known countries having occurrences of commercial significance. The classic locality is Sweden's Utö Mines, which, although reportedly still containing considerable petalite, have been closed and are not expected to be operated in the near future. At Varuträsk, in northern Sweden, petalite carrying 4 pct lithium oxide is the main ore. In 1946 there was reported about 1000 tons on hand. However, the iron content was 0.60 pet too high for other than chemical use. Petalite has been reported in western Australia. At the Cottesloe mine, where small quantities have been reported available, it is produced in conjunction with feldspar. Petalite occurs in considerable quantity in the feldspar quarry at Londonderry, and it was estimated1 in 1943 that over 3700 tons might be available. The petalite in South West Africa was first discovered by F. J. Jooste, a lawyer by profession, in 1938. The following year he discovered a much larger deposit, and in 1948 another important discovery was made. These deposits occur near Kari-bib and constitute the only known commercial deposits. Their full extent has not yet been determined, but huge massive blocks of petalite of the purest grade, running into many thousands of tons, can be seen in all these deposits. To date, 60,000 tons of high grade, low iron containing ore has been blocked out in the major bodies. Mining for years to come will be confined to simple quarrying. Selection from accessory minerals has proved

Jan 1, 1951

By J. D. Clark

ONE'S lifetime does not usually offer the oppor-tunity to observe and be a part of the commercial development of an entirely new material. Petalite has been known for over a century, but at first it was presumed rare. However, it was found to be so abundant that it has become a new and extremely useful industrial tool. Mineralogy Petalite is a lithium-aluminum-silicate mineral. It was from petalite that J. A. Arfwedson first discovered lithium in 1818. The theoretical composition of Li2O • A12O8 • 8SiO2 is equivalent to 78.4 pct silica, 16.7 pct alumina and 4.9 pct lithia. The mineral in its known commercial occurrence is colorless to white and rarely gray, transluscent and rarely transparent. It is brittle, has a vitreous luster, and occurs usually in cleavable masses (fig. 1). It is classified as a di-silicate, but is similar in composition to the metasilicate spodumene, Li2O.-Al2O8-4SiO2 (table I). However, their specific gravities are quite different (3.13 to 3.20 for spodumene, 2.39 to 2.46 for petalite). Occurrence Petalite specimens have been reported in many localities; however, there are only three known countries having occurrences of commercial significance. The classic locality is Sweden's Utö Mines, which, although reportedly still containing considerable petalite, have been closed and are not expected to be operated in the near future. At Varuträsk, in northern Sweden, petalite carrying 4 pct lithium oxide is the main ore. In 1946 there was reported about 1000 tons on hand. However, the iron content was 0.60 pet too high for other than chemical use. Petalite has been reported in western Australia. At the Cottesloe mine, where small quantities have been reported available, it is produced in conjunction with feldspar. Petalite occurs in considerable quantity in the feldspar quarry at Londonderry, and it was estimated1 in 1943 that over 3700 tons might be available. The petalite in South West Africa was first discovered by F. J. Jooste, a lawyer by profession, in 1938. The following year he discovered a much larger deposit, and in 1948 another important discovery was made. These deposits occur near Kari-bib and constitute the only known commercial deposits. Their full extent has not yet been determined, but huge massive blocks of petalite of the purest grade, running into many thousands of tons, can be seen in all these deposits. To date, 60,000 tons of high grade, low iron containing ore has been blocked out in the major bodies. Mining for years to come will be confined to simple quarrying. Selection from accessory minerals has proved

Jan 1, 1951

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