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By E. O. Kirkendall

THE investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,' particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize; it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosenhain,2.3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,7 and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,' and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. EXPERIMENTAL PROCEDURE This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ±3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 34 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photo-micrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 3a hr. at 300°C. It was then etched in 25

Jan 1, 1942

By E. C. Bohlen, H. l. Burghoff

The work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and G1ocker;l Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45' to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (II3)[II2], (ooi)[ioo], and a combination of (II0)[II5] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,' who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. Test Materials and Equipment For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, I31/2 in wide and I1/2 in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942

By Alfonso Rizo-Patrón, A. M. Gaudin

PREVIOUS studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I : I ratio of collector ion to activator ion gives optimum results, and that a 2:I ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. APPARATUS AND SUPPLIES The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel stator, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker's analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker's analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1942

By G. S. Scott, G. W. Jones

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By John T. Galey

The outstanding developments of the year in southwestern Pennsylvania were the establishment of the Summit Fayette County gas pool and the gas pool in Nicholson township, Fayette County, and Monongahela township, Greene County, as major producing areas, and the indication of four new shallow gas pools. Curtailment of drilling for shallow gas is expected to follow order M68 of the Office of Production Management. Gas completions were approximately 70 per cent higher, oil completions nearly 25 per cent lower, dry holes were unchanged and drilling wells as of Dec. 31, 1941, nearly loo per cent higher than last year. Shallow Development Oil.—Outside Butler County, only 11 producers were drilled, with a total initial of 221 bbl. The best of these was in a portion of Gilmore township, Greene County, which ordinarily produces gas. This well flowed 77 bbl. in 11 hr., along with about one million cubic feet of gas from the Fourth (U.Dev.) sand. Washington County had a 10.20 and a 25-bbl. well in Morris township and a 20-bbl. well in South Franklin township. These were all in the Fifth Sand. The price of oil to Jan. 27 was $1.80 per barrel, when a 15¢ increase was made. This was followed by a raise of 20¢ on Apr. 23, 15¢ on May 21, 20¢ on June 18 and 25¢ on Aug. 14. The last increase was canceled on Aug. 23 by the Office of Price Administration, which pegged southwestern Pennsylvania crude at $2.40 per barrel. Gas.—An almost doubled initial production of natural gas is the result of the large increase in number of wells drilled. The outstanding discovery of the year was in the vicinity of Armbrust, Hempfield township, Westmoreland County, where a well drilled to what at first was considered the Bayard sand, but what is now known to be the Fifth (U.Dev.) sand, at 2100 ft. found nearly 5 million cu. ft. of gas. Since this completion 14 wells have been finished, only one of which was dry, giving a combined total open flow of approximately 15 million cu. ft. The sand is 35 to 40 ft. thick and the saturation extends through most of that thickness. Rock pressure, which is 1040 lb. per sq. in., is abnormally high. An area of only about one square mile has been proven but some of the 24 new wells drilling as of Dec. 31 will no doubt extend it considerably. This development has taken place in an area heretofore considered to have had little prospect. There were three good wells in other parts of Westmoreland County. One well in Franklin township, which had 12 million cu. ft, of gas in the Fifth sand, was entirely surrounded by dry holes but is still pro- . ducing at a high rate. In Bell township a 1.6 million cu. ft. well was found in the Speechley (U.Dev.) sand and in Washington township the same sand produced 2.7 million cu. ft. with shut-in pressure of 970 Ib. at 2820 ft. This well is offset by two dry holes and one well with a capacity of only 10 M cubic feet.

Jan 1, 1942

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By R. F. Mehl, G. V. Smith

THE decomposition of austenite in steels, because of its immense practical importance, has been subjected to extensive study in recent years from the point of view of the mechanism of the process.1-3 Although much information has been acquired a number of questions, principally of theoretical interest, remain. One is that of the atomic-crystallographic mechanism by which each of the various reaction products forms. The isothermal reaction products of the eutectoid decomposition in plain carbon steels (to which this study is restricted) have conveniently been classified in three general groupings-pearlite, bainite, and martensite. Of these several products, pearlite and martensite have been studied extensively, but bainite has received only scant attention. As a result, the mechanism of the formation of pearlite and that of martensite are now fairly well understood while a great deal of uncertainty exists regarding bainite. PEARLITE Pearlite forms from austenite by the precipitation of alternate platelets of cementite and ferrite, which grow into the austenite matrix.2-5 The rate of reaction may be described in terms of a rate of nucleation and a rate of growth 2 3 Mehl and Smiths have attempted to determine the lattice relationships existing between the ferrite in pearlite and the parent austenite. Using a pole-figure method of analysis, it was found that a limited number of ferrite orientations resulted from the decomposition of a single grain of austenite; it was not possible,[ ]decide between two assumed ideal relationships, both of which appeared to account for the experimentally determined pole figure. It was definitely shown, however, that the relationship obtaining was quite different from that determined for the proeutectoid separation of ferrite.7 No attempt was made to determine the habit plane (matrix plane to which the precipitate lies parallel) of the pearlite lamellae. Belaiew8 earlier had stated that the number of directions assumed by the pearlite lamellae in a single grain of austenite was 12 (no details were given) and concluded wrongly, as Mehl and Smith' have pointed out, that the lamellae delineate the {210} planes of ferrite.* MARTENSITE It is known that martensite is a transitional constituent of body-centered tetrag-

Jan 1, 1942

By Harvey S. Mudd

AMONG the highly skilled craftsmen of the Renaissance were those who worked with ores and metals. The author of this book, Vannoccio Biringuccio, was a master craftsman in the practices of smelting and of metalworking. Contrary to the customs of a trade, Biringuccio was moved to impart his knowledge to all and thus he has given us the earliest hand- book on metallurgy-in fact, the first printed book dealing with the applied metal arts and the processes of ore reduction. We should remind ourselves that metallurgy is an ancient art and then it fair1y may be said that Biringuccio sought to describe the techniques that had been in course of development since the Bronze Age of western civilization. Whether Biringuccio was a man of learning or a scholar according to the standards of his time we do not know, but today we recognize him as a man of science who gave his wisdom to succeeding generations. It was not until the coming of the Power Age at the end of the eighteenth century that progress was resumed in the science of which he wrote more than two hundred years before. Little is known of Biringuccio's training in his native Siena. It can be surmised that there, as in Florence, where his contemporary Benvenuto Cellini lived, he received his training in the craftsman shops where the industrial arts were taught and flourished alongside the fine arts. Perhaps he and Cellini were acquainted, although there is no mention of Biringuccio in Cellini's autobiography-an omission that Cellini's vast egotism makes understandable. He was the great artist, and Biringuccio was a practical, studious, unromantic figure with no favors to dispense. In the April 1940 issue of Mining and Metallurgy Dr. Smith describes Biringuccio's book under the title of "A Neglected Italian Metallurgical Classic." The article, revised and extended, forms the basis of the introduction to the present volume, and I urge all who take up Pirotechnia to read what Dr. Smith has written in the Introduction. Biringuccio's work is a classic and in its translation Dr. Smith and Dr. Gnudi have brought to bear the high degree of scholarship that it deserves. Dr. Gnudi made the translation at Dr. Smith's request and it was then refined "in the fire" of his scientific knowledge of the subject. The result is a book which the Institute is proud to place before its members and which the Memorial Fund Committee considers it a privilege to publish.

Jan 1, 1942

By Irving M. Symonds

COMPAÑIA Minera de Peñoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Providencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Peñoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreón, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. ORE TREATED The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopyrite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I. [ ]

Jan 1, 1942

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Jan 1, 1942

By F. M. Walters

IN order to isolate the effect of an element on some property of an alloy, the effect of the other alloying elements must be elimi- [ ] nated, either by reducing their quantity to the extent that they may be neglected or by determining the specific effect of each. The success of Grossmann1 in calculating [ ] hardenability from chemical composition by means of factors suggested such a

Jan 1, 1942

By Francis M. Walters, Irwin R. Kramer

The substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient 01 expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and their use up to 400' or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. Experimental Methods Two methods were used in studying the stability of the low-expansion iron -nickel-cobalt alloys. Dilatometer specimens were held at 480°C. for 9 months and the change in expansion characteristics was dctcr- mined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1942

By M. F. Trice

Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

AS you and anyone else can understand, a great expense and a large supply of things are necessary for parting a quantity of silver by means of aqua fortis. First, as you have seen, it is necessary to have a great abundance of every kind of cucurbit and alembic, of charcoal and wood, and a large number of pounds of a vigorous, well-purified aqua fortis, because for every pound of silver there are of necessity [71v] at least four pounds or more employed from the parting to the coloring of the separated gold. It is also necessary to prove its fineness and to granulate or beat it, to have furnaces and supplies, and to provide for a thousand other necessities which need not be repeated now. The most important thing in this art seems to me to be that it requires continual working night and day with extreme watchfulness and care. For this reason another way, much quicker, less dangerous, and less expensive than the aforesaid one was found by some clever men (alchemists, I believe) in order to avoid such laborious and heavy methods. It produces the substance of the thing exactly as the acid does. If you wish to make use of it in conjunction with the acid it is possible to render great aid to this work although there is a great difference in the techniques of the two. The method used in this parting is as follows: First, make a round or square wind furnace for melting, below ground or above, and of height and size in proportion to the work and as it comes out best for you. Then take a large clay crucible and fill it almost up to the edge with that silver which contains the gold, cut into pieces, and put it to melt with the silver on top of a piece of brick cut to the size of the bottom of the crucible and resting on a grate in the middle of coals that are burning well. When you see that the silver has been made so hot by the fire that it looks white and that it wishes to begin to liquefy, take a little stick of sulphur or a small piece of antimony and put it in. When this is melted, lifting away the charcoal that covers it, put in more sulphur or antimony (for the method is the same with either one) until the silver is very well melted and these materials properly incorporated. Then for every pound of silver that you put in add half an ounce of sheet copper. When this is melted take your crucible out with tongs or pincers and strike the bottom gently on the coals two or three times so that the gold may make a residue on account of

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

THE second operation in the art of casting, and one of the greatest importance, is that of melting and thoroughly liquefying the materials of which you wish to make your casting. On this operation depends the whole outcome of your intentions and the perfection of your work. Without it, even though you had a great abundance of moulds and vast quantities of bronze, your desires, labor, and expense would all be in vain. In this operation I find on consideration that, in addition to experience, there are three necessities-perhaps indeed four-that must be provided without fail. The first is the furnace or other agent which contains the fire and the metal brought together. The second is the wood or charcoal which is the necessary and proper nutriment of the fire, from whose virtues are derived the greater or lesser forces which, according to their kind, are ready to effect what is required. The third is to have the materials disposed to easy fusion by means of corruption, alloying, or by their own nature. The fourth, as the motivating cause of the whole, could perhaps be listed as the first-this is the ingenuity and good judgment of the worker, together with the bodily exertions not only of himself but also of his helpers in addition. For, besides a certain ordinary caution, it is necessary to pay particular attention, first, to see that the furnaces, machines, ladles, hearths, refineries, and other kinds of instruments or similar vessels be made so as to dispose the metals for melting, and, when melted, that they easily maintain them so. These should also be prepared in such a way that they cannot be injured by the fire, for if they should be damaged the operation would fail. In order to do this, it is first necessary that you arrange the instruments with forethought and action so that the power of the fire can operate. Fire operates on things only when brought together with them in long-continued operation, or when driven by a great force of wind. It burns many things and softens others, but it makes the metals as liquid as water.

Jan 1, 1942

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

IDO not want to omit anything in which fire or its operation has a part, if I know or can tell it, and have already told you so many other useful, powerful, and ingenious effects (finally of powder and other' fire deadly and very injurious to all living things, indeed, composed for the destruction of those who possess it as well as those who do not) but I do not want the end of my writing to be in tragedy. Therefore I wished to tell you how, from these fires composed of forceful and horrible mate¬rials bringing harm and terror to men, a happy and pleasing effect is also produced and, instead of fleeing from it, the people willingly go to see it. Among others I remember that it was once customary to use these in Florence and in Siena, more than elsewhere. The chief feast day celebrated. by one of these cities is the day of the birth of Saint John, and the other is the Assumption of Our Lady, on the fifteenth of the month of August. In the morning they visit the shrines with great devotion and solemnity, displaying their pomp as much as possible, and later they hunt lions, wild bulls, untamed horses, and many other animals. In the same public squares there was also erected as a decoration an edifice fixed in the ground in the middle of this space, or hanging from a heavy rope crossing between the loftiest points of equal height that could be found in that place. This they have done and still do, and perhaps in time to come will continue to do when opportune. This structure was usually of wood; indeed it is necessary that the latticework of its construction be made only of this. It was covered and en¬larged by tying and fastening hay on top to bring it almost to completion and then papier-mâché was applied. [165v] The figures were first appropriately painted and made of a combination of vessels one above the other, developing various decorative figures in relief which should represent some fable or history and should not appear haphazardly made or without understanding. Now the master proceeded to arrange these figures in a composition according to his skill or art of design, and likewise planned

Jan 1, 1942

The only real data available begin in 1873. The total figures are all estimated from these. [ ]

Jan 1, 1942

The Institute maintains a dual relationship with students: (1) an individual relationship with a Student Associate; and (2) a relationship with local organizations of students, known as Affiliated Student Societies or Student Chapters. 1. The conditions of Student Associateship are set forth in Section 9, Article I, of the Bylaws of the Institute (see page 62 and following pages). During 1934, sundry amendments were made for the purpose of improving the student relationship. Postgraduate students are now eligible; and associateship can be maintained, with the payment of the regular dues of $2 per year, for 18 months following graduation in June. With his regular dues, each Student Associate is entitled to receive during the year his choice of MINING AND METALLURGY, METALS TECHNOLOGY, MINING TECHNOLOGY, PETROLEUM TECHNOLOGY, or two "classes" of Technical

Jan 1, 1942