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By T. S. Lundy, R. E. Pawel

Effects of short-circuiting paths on observed diffusion behavior in real crystalline systems are considered. It is concluded that experimentally measured diffusion coefficients may vary widely from values associated with true lattice diffusion to those appropriate for short-circuiting paths alone depending upon the conditions of the experiment and the sensitivity and completeness of the data. IN 1961 Harrison1 classified experimentally observed diffusion behavior in systems involving both lattice and dislocation-enhanced atomic transport into three categories. His types A and C were limiting cases where the measured diffusion coefficients using the usual serial sectioning techniques were representative of lattice diffusion (with only slight effects of dislocations) and dislocation-network diffusion (with only slight effects from lattice diffusion), respectively. In both cases A and C for a sectioning experiment in which the diffusion couple has the semi-infinite geometry and unidirectional diffusion takes place from a plane source located at the origin of the coordinate system, he pointed out that Gaussian penetration behavior should be observed. For case A the lattice coefficient should be slightly enhanced by dislocation contributions, and the model of Hart2 can be used to predict the amount of this enhancement. For case C the observed coefficient should be that for the dislocation network and have little or nothing to do with lattice diffusion. Hart's model in its general form is still applicable, but the apparent diffusion coefficient for this case is virtually independent of dislocation density. Harrison's case B is that for which non-negligible contributions exist for transport by both mechanisms and "the concentration distribution does not approximate to any simple form." With the possible exception of very low temperatures where diffusion distances approach atomic dimensions, any real diffusion specimen will in general show non-Gaussian behavior provided the data are complete enough to uncover it. Thus, a "complete" set of data for any real system cannot be expected to be totally amenable to treatment by a simple mathematical model which does not take into account the relative distribution of transport by the various modes or submodes. For a particular sensitivity of specimen analysis and at a given temperature of annealing if the concentration profile could be observed as a function of time, "the behavior will initially be type C, and will develop into type B. and ultimately type A".1 Thus, it appears that the type of diffusion behavior which is experimentally observed in a given system depends very much upon the particular experimental conditions and the particular tools available to obtain the data. Interpreted in this fashion, Harrison's classification refers not to the diffusion behavior as a whole but to the relative sensitivity of the method of examination and completeness of the data. In the present paper we will: 1) assume that the measured penetration behavior follows the same general classification as that proposed by Harrison; 2) give, for diffusion in tungsten, examples of the range of diffusion coefficients that it is possible to obtain in a single experiment; and 3) speculate that some arguments which consider the possibility of short-circuiting effects being responsible for "anomalous" diffusion in several bcc metals may have been discarded prematurely.3 Both monocrystalline and polycrystalline tungsten were used in this work. The former was obtained as triple-pass, electron-beam zone-refined 6.0-mm-diam rod from Materials Research Corp.. Orange-burg. N.Y. The latter was swaged, high-purity bar stock which was annealed for 2 hr at 2200°C and 10-9 torr to yield an average grain diameter of about 25 /i. The tracer Nb95 was received in oxalate solution from the Isotopes Division, Oak Ridge National Laboratory. Experimental procedures of specimen preparation, isothermal diffusion annealing, serial sectioning by anodizing-and-stripping, and y counting of the individual sections to determine the tracer penetration profile after a given diffusion anneal have been described elsewhere.4 However, it should be noted that the anodizing-stripping sectioning technique has the particular advantage for this research of permitting sectioning to be accomplished over a wide range of

Jan 1, 1970

By Anderson, Burton E.

FOR several centuries diamond mining has been an adventurous, profitable and enticing industry in Brazil. Some of the world's most valuable diamonds have been found in this country. Two of the most famous stones are the "Estrella do Sul" (Southern Star), weighing 2541/ karats, and the "Branganca," weighing 1680 karats in the rough and 367 karats cut. For a great number of years the stones extracted and sold were mostly the white diamonds used for jewelry. Within the last thirty years black diamonds have been developed as an abrasive cutting material and in these black diamonds the State of Bahia, Brazil, has a monopoly of the world supply. Carbons, as they are commonly called, are being used for core-drilling, polishing, cutting, wire-drawing, and vari-ous other applications in which such a hard substance is required. Bernard Bandler & Sons, of New York City, have selected, graded and delivered these carbons to the United States markets.

Jan 1, 1932

By J. W. Rutter, K. T. Aust

THE object of the experiments to be described in this report was to determine, first, which grains, out of a large number introduced into a sample in which their growth could proceed, were able to grow most successfully; and, second, the factors which control their growth selection. In an earlier study of grain boundary migration in high-purity lead,' it was found that, under some conditions, the most successful grain in an experiment of this type bears a special orientation relationship to the grain into which it is growing. The present work represents an extension of the previous study, directed at the determination of the orientation relationships which appear under a wider variety of conditions. Experiments of this general type have been done using commercial aluminum2 with somewhat conflicting results. In the present experiments, in contrast to the above,' the sample composition was a principal controlled variable, resulting in a considerable clarification of the phenomena observed. EXPERIMENTAL TECHNIQUE The experimental technique used in this investigation was essentially that employed previously in studies of grain boundary migration kinetics.1'3 The material used was zone-refined lead with various small amounts of tin or silver added to study the effect of varying the sample composition. The specimens were in the form of single crystals, about 1/4 in. 1/4 in cross section by 3 to 4 in. in length, grown from the melt in a horizontal graphite boat. A crystal grown in this way generally contained a lineage or "striation" substructure of the type shown in Fig. 1 of Ref. 1. This substructure consists of an array of low-angle boundaries which partition the crystal into regions misoriented from each other by a few degrees. The substructure constitutes a source of driving energy, estimated to be about 4000 ergs per cc, for the migration of a large-angle grain boundary into the striated crystal. New grains were introduced by plastic deformation in compression of a localized reglon at one end of the sample. Re-crystallization occurs at room temperature in the deformed region, introducing a large number of new, striation-free grains into the specimen. These grains are able to grow into the melt-grown crystal on annealing at a suitable temperature. The stria-tions are removed by passage of the grain boundary, as the substructure energy is utilized to produce the boundary migration. Usually, only one or two of the recrystallized grains persist after growth has occurred for about 1 cm out of the deformed region. Laue back-reflection X-ray photographs were obtained to determine the orientation relationship between the melt-grown crystal and the recrystallized grain or grains which grew most successfully in each specimen. EXPERIMENTAL OBSERVATIONS Fig. 1 shows the results obtained for a series of specimens to which had been added tin in the range from 0 to 5 ppm by weight. In this figure is plotted, in the standard stereographic triangle, the single axis about which the most successful recrystallized grain or grains are related to the starting, melt-grown crystal by the smallest rotation. The range of angular rotations observed about such axes is indicated beside each stereographic triangle. The results shown in the stereographic triangle on the left, Fig. l(a), were obtained by localized deformation at one end of each specimen at room temperature, followed by annealing in a furnace which had been preheated to 300°C. The furnace atmosphere was argon. It will be seen that the orientation relationships observed between the melt-grown and recrystallized grains are quite random. On the right, Fig. l(b), are shown results for samples in which the de-

Jan 1, 1961

By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

By F. C. Bond

SIZE of grinding media is one of the principal factors affecting efficiency and capacity of tumbling-type grinding mills. It is best determined for any particular installation by lengthy plant tests with carefully kept records. However, a method of calculating the proper sizes, based on correct theoretical principles and tested by experience, can be very helpful, both for new installations and for guiding existing operations. As a general principle, the proper size of the make-up grinding balls added to an operating mill is the size that will just break the largest feed particles. If the balls are too large the number of breaking contacts will be reduced and grinding capacity will suffer. Moreover, the amount of extreme fines produced by each contact will be increased, and size distribution of the ground product may be adversely affected. If the balls added are too small, grinding efficiency is decreased by wasted contacts that are too weak to break the particles nipped; these largest particles are gradually worn down in the mill by the progressive breakage of corners and edges. Ball rationing is the regular addition of make-up balls of more than one size. The largest balls added are aimed at the largest and hardest particles. However, the contacts are governed entirely by chance, and the probability of inefficient contacts of large balls with small particles, and of small balls with large particles, is as great as the desired contact of large balls with large particles. Ball rationing should be considered an adjunct or secondary modification of the principle of selecting the make-up ball size to break the largest particle present. Empirical Equation In 19521,2 the author presented the following emerical equation for the make-up ball size: B - ball, rod, or pebble diameter in inches. F = size in microns 80 pct of new feed passes. Wi - work index at the feed size F. Cs - percentage of mill critical speed. S — specific gravity of material being ground. D == mill diameter in feet inside liners. K - 200 for balls, 300 for rods, 100 for silica pebbles. Eq. 1 was derived by selecting the factors that apparently should influence make-up ball size selection and by considering plant experience with each factor. Even though Eq. 1 is completely empirical, it has been generally successful in selecting the proper size of make-up balls for specific operations. But an equation based on theoretical considerations should be used with more confidence and have wider application. The theoretical influence of each of the governing factors listed under Eq. 1 was accordingly considered in detail, as described below, and a theoretical equation for make-up ball sizes was derived. Derivation of Theoretical Equation Ball Size and Feed Size: The basis of this analysis is that the largest ball in a mill should be just sufficient to break the largest feed particle into several pieces, excluding occasional pieces of tramp oversize. In this article the size F which 80 pct passes is considered the criterion of the effective maximum particle feed size. The smallest dimension of the largest particles present controls their breaking strength. This dimension is approximately equal to F. As a starting point for the analysis it is assumed that a 1-in. steel ball will effectively grind material with 80 pct passing 1 mm, or with F- 1000µ or about 16 mesh. The breaking force exerted by a ball varies with its weight, or as the cube of its diameter R. The force in pounds per square inch required to break a particle varies as its cross-sectional area, or as its diameter squared. It follows that when a 1-in. ball breaks a 1-mm particle, a 2-in. ball will break a 4-mm particle, and a 3-in. ball a 9-mm particle. This is in accordance with practical experience, as well as being theoretically correct. Confirmation of this reasoning is supplied by the Third Theory of Comminution," which states that the work necessary to break a particle of diameter F varies as F. Since work equals force times distance, and the distance of deformation before breaka4e varies as F it follolvs that the breaking force should vary as F½ These relationships are expressed in Table I, with a 1-in. ball representing one unit of force and breaking a 1-mm particle. This establishes theoretically the general rule used in Eq. 1 that the ball size should vary as the square root of the particle size to be broken. Ball Size and Work Index: The work input W required per ton" varies as the work index Wi, and the

Jan 1, 1959

By R. S. Bradley

WHAT are known as insulating firebrick are lightweight firebrick with low thermal conductivity designed primarily for use in direct contact with furnace gases. These are a recent development in the refractories industry, and are really an outgrowth of the type of insulating brick suitable for use behind refractory walls developed by the insulation manufacturers. To differentiate between these two types of brick, the manufacturers have recently agreed upon the use of the term "Insulating Firebrick" to apply to the type of brick suited for use in direct contact with furnace gases, and the term "Insulating Brick" for the type suitable for use behind refractory walls. Insulation was applied to steam pipes as far back as 1900. This was a low-temperature insulation, the most common type being magnesia blocks. The next development was applying insulation to the outside of furnace walls, a service which necessitated an insulating material of higher temperature resistance. Natural diatomaceous earth, both in the powdered and brick form, was used; this was efficient and is still used extensively for backing up refractory walls where the inner surface temperature of the insulation does not exceed 1600° F.

Jan 1, 1937

By Hermsdorf, Richard P. E.

AMONG the newer lead smelting and refining plants of the country is that of the United States Metals Refining Co., at Carteret, N. J. Not only is the technical practice here modern and efficient, but exceptional care is taken to assure healthful operating conditions for the employees. One large building houses the entire department, which includes, as its chief units, one reverberatory smelting furnace, one blast furnace, two softening furnaces, one utility reverberatory furnace, two Faber du Faur retorts, five 120-ton kettles, three 60-ton antimouial lead kettles, and one 5-ton kettle for experimental purposes. There is a 10-ton overhead crane in the kettle aisle, which is also used for shipping lead. Other auxiliary equipment is referred to in the outline of operations. A general plan of the plant is shown in Fig. 2, and a general view in Fig. 1. Primary smelting operations are conducted in a 30 by 11-ft. reverberatory furnace with bottom, roof, and upper walls of clay brick, magnesite

Jan 1, 1934

PRESIDENT GEORGE OTIS SMITH, District 4 WASHINGTON, D. C. PAST PRESIDENTS SAMUEL A. TAYLOR, District 3 PITTSBURGH, PA. E. DEGOLYER District 0 NEW YORK, N. Y. FIRST VICE-PRESIDENT W. H. BASSETT District 1 WATERBURY, CONN. TREASURER KARL FILERS NEW YORK, N. Y.¬ SECRETARY H. FOSTER BAIN NEW YORK, N. Y.

Jan 1, 1923

President H. M. Howe, Boston, Mass. (communication to the Secretary): Le Chatelier's pyrometer is certainly a most convenient and accurate instrument for the laboratory, and one that may be used under some conditions in the mill. I have used it for several years and with great satisfaction. Like Prof. Roberts-Austen and unlike Herr Blass, I have always found that its indications remain constant over long periods. Like Prof. Roberts-Austen, also, I find it possible, in a quiet place, to read with extreme accuracy ; and, by the use of a telescope, I can read temperatures to within a degree, for some delicate determinations which I have in hand. Variations in the temperature of the room affect the readings of the instrument far less than one would expect. When the current is cut off, the mirror does not always return exactly to the same place; in other words, the zero shifts appreciably, and must be determined often, indeed every few hours if accuracy be desired. In some cases I have had it determined within a very few minutes of every important reading. To this end a switch should he introduced, so that the circuit may be broken readily. With this arrangement we can determine accurately the position of the zero within a very few seconds of the time of taking any especially important reading. The chief causes of the variation of the zero which I have noticed are as follows: a. The suspension may not be tight enough, so that the momentum of the galvanometer frame as it swings makes its supporting wires slip in their bearings. b. Changes in the position of neighboring iron objects may deflect the mirror. c. Changes in the temperature of the room may, perhaps, change the torsion of the suspension wires, and so shift the mirror. d. Dust may attach itself to the galvanometer frame, and by friction against the surrounding fixed parts of the galvanometer, may

Jan 1, 1895

By Butler, P. B.

TRIPOLI is a rather unusual form of silica, which thus far has been found in commercially valuable quantities only in the neighborhood of Seneca, Mo., although there are numerous deposits of somewhat similar materials in several southern states. The latter have not, however, attained any position of real importance, due undoubtedly to definite structural limitations which have rendered them less suitable for the particular uses that have given tripoli its principal outlets. Raymond B. Ladoo, mineral technologist, says': "Since that time (1880-90) the term tripoli has with increasing definiteness been reserved for the Seneca material, and other siliceous materials of similar origin and physical properties."

Jan 1, 1928

Technical graduate wanted for metallurgical. work in experimental laboratory of large New England manufacturing concern. A knowledge of metallography of steel is essential. Practical experience is desirable but not required. No. 305. Man familiar with precipitating with the diamond drill core to act as foreman. No. 311. Competent mining man to develop and take charge of mines in Peru. Property to be developed from start and equipped with thoroughly modern appliances to meet the increased production. Applicant must possess considerable mechanical ability and experience. No. 312. Engineers and assistant engineers in forest production for National Defense work for the duration of war. Laboratory work conducted primarily by experimental and research methods, embracing principally investigations of mechanical and physical properties of wood, processes for the preservation of wood against decay and other destructive agents, practical problems of pulp and paper industry, and other industries utilizing wood by chemical means or otherwise. Assistance in this department of Government is urgently required in order to obtain maximum benefits from the investigation. Salary $1860 to $3000 for engineers; $1200 to $1800 for assistant engineers. No. 313.

Jan 6, 1918

By E. H. Griswold

PETROLEUM production engineering is essentially the application of the laws of 'physics and mechanics to the production of oil. A true production engineer is one who can apply the principles of mechanics, hydraulics, thermodynamics, and other physical arts so as to facilitate' the efficient and economical recovery of oil. To this end he must have wide knowledge of practical field operations and a working knowledge of geology, with a thorough understanding of the underground state of the fluids which he seeks to control. Generally speaking, there have been two schools of production engineering, the California development and the Mid-Continent development. In California the preliminary production engineering was done by representatives of the U. S. Bureau of Mines and the State Mining Bureau, and was essentially subsurface work in regard to casing patterns, water shut-offs, and completion procedure, inasmuch as these were problems of the utmost immediate importance to the California industry. The oil companies were impressed with the value of such work and placed engineers, or more strictly speaking, engineering geologists on their field staffs. These men, realizing the need of further technical study in the mechanical phases of producing operations, added mechanical and mining engineers, and out of the blend developed what is now known as a production engineer.

Jan 1, 1932

By Francis M. Walters

IN spite of the war and the preoccupation of many physical metallurgists with work on secret or confidential problems, definite progress was made during 1944 in our understanding of the behavior of steel and of the effect of alloying elements. During the first two years of the war there was much concern over the possible unavailability of certain alloying elements; this period saw the development of the N.E. (National Emergency) steels. However, the measures taken eased the alloy situation and currently, highly practical problems under study are the graphitization of low-carbon steel and weld-cracking, while investigations of more theoretical interest have concerned hardenability, isothermal reactions, the effect of hydrogen and the interpretation of the notched-bar impact test.

Jan 1, 1945

By T. S. Lovering

GEOCHEMICAL prospecting extends the age-old method of searching out lodes with a gold pan and rationalizes the prospector's hunch that certain plants are associated with ore. It uses sensitive but cheap and rapid analytical methods to find the diagnostic chemical variations related to hidden mineral deposits. Exploration geologists can gain tremendous assistance from this new tool, although its optimum use is not simple. To bring out the geochemical pattern that reveals the presence of a hidden ore deposit with a minimum number of samples requires a combination of shrewdness, chemical knowledge, and exploration geology. The use of sensitive analytical methods for prospecting had its start in the 1930's in northern Europe, where Scandinavian and Russian geologists had some success in these early efforts. Very little geochemical prospecting was carried on in the United States at this time, and no sustained interest was manifest until the close of World War 11, when geochemical investigations were started by the Mineral Deposits Branch of the U. S. Geological Survey. The purpose of these investigations was to apply geochemical principles and techniques to surface exploration for mineral deposits. Both the research on analytical methods and the routine trace analyses for field investigations were at first conducted by a single group, but it later became apparent that the trace analyses could be done by men of less experience than that required for successful research on methods. For the past several years there have been two groups of chemists, and although their functions overlap, three of the chemists are chiefly concerned with research, while four to six other men make the trace analyses for field projects. The chemical investigations, as well as the field projects of the Geochemical Exploration Section, concern only those phases of the subject that are appropriate to a government organization; every effort is made to help private industry, but not to compete with it, in finding orebodies. The chief aim of the Section, therefore, is to develop new analytical techniques and publish the results promptly, to carry out field investigations of the fundamental principles of geochemical dispersion, and to field test promising- techniques under controlled conditions. Some routine geochemical exploration work is carried on in connection with DMEA loans, and in district studies where the project chief wishes geochemical information on certain areas for his report. It should be emphasized, however, that geologists of the Geochemical Exploration Section are primarily concerned with fundamental principles underlying the distribution, migration, and concentration of elements in the earth's crust. To facilitate the use of geochemical methods the USGS has published much information on its methods of analysis and has provided opportunities from time to time for qualified professional personnel to study these methods, to work in the USGS laboratory, or to attend demonstrations of the analytical techniques at the Denver Federal Center. Typical of the research carried on are the problems now being investigated: 1) Development of rapid and sensitive analytical methods suitable to the determination of traces of metals and other minor elements in various materials, such as rock, soils, plants, and water. At the present time attention is being concentrated on U, Bi, Cr, and Hg, and satisfactory rapid trace analytical methods are virtually perfected for U and Bi. Good methods are also available for: Cu, Zn, Pb, Ni, Co, As, Sb, W, Mo, Ag, Nb, Ge, V, Ti, Fe, Mn, S, and P. 2) The relation of geochemical anomalies in plant materials to the geochemical distribution of elements in soils surrounding the plant. 3) A study of the dispersion halos in transported sedimentary cover such as glacial drift and alluvium over known orebodies. 4) A study of the behavior of ore metals in the weathering cycle. 5) A study of the behavior of the ore metals during magmatic differentiation. This requires a study of the distribution of minor metals in fresh igneous rocks and their component minerals in a well established differentiation series and in adjacent country rock. 6) A study of the dispersion of metals in primary halos in the wall rock surrounding orebodies. 7) Regional and local studies of the metal content of surface and groundwater in mineralized and barren areas. Many field projects of the Mineral Deposits Branch also require the services of USGS chemists during their investigation of the geochemical environment of ore deposits. From the work that has been done certain general principles have emerged. Concentrations of an element that are above the general or background value of barren material are called positive geochemical anomalies or simply an anomaly, whereas values less than background are called negative anomalies. The anomalies most commonly investigated in geochemical prospecting are those formed at the earth's surface by agents of weathering, erosion, or surficial transportation, but more and more attention is being given to primary anomalies found

Jan 1, 1956

By J. F. K. Brown

ANTHRACITE in 1943, in common with the coal industry as a whole, passed through a year of wage negotiations that seemed endless. In the early months discussion of the United Mine Workers' demands was taken up and carried on continuously until May, finally reaching an impasse when the Union refused to continue at work, while submitting their demands to the War Labor Board. Thus a strike threatened, averted by the Federal Government taking over the industry, effective May 1, by order of the President. An office of the Bureau of Mines was established in Wilkes-Barre under the direction of J. J. Forbes, Mineral Production Security Division, as regional manager, who conducted operations until September, 1943, when the collieries were turned back to the operators. But the miners did not agree with the War Labor Board's award rendered in the fall, resulting in a recurrence of the previously threatened strike. again averted by Government control. In addition to the major upsets, a number of individual suspensions occurred at various mines. In spite of these drawbacks, to which might be added the difficulty of obtaining equipment and the scarcity of man power, the industry by November was only little less than a million tons short of the previous year. and in all probability, finally produced but little less than in 1942. This little less. however, was greatly missed in the market.

Jan 1, 1944

By Zhu Weishen, Xu Dongjun

In the 1st part of this paper a comparassion of the different methods for determining the modules of elasticity and deformation of hard rock is made. It is found that the plate bearing method has a serious shortcoming. The slit flat-jack method seems to be a mare reasonable technique, which is recommended as a desirable method for in situ testing. In the 2nd part, a new test method to determine the properties of deformation and strength of weak plane in rock mass is recommended. Then the relation of weak plane character to the character of stress-strain curve, the relation of normal stress to the character of shear displacement curve and the yielding criterion of weak plane are discussed.

Jan 1, 1982

FROM newspaper reports circulated in Indonesia, it seems quite obvious that many people, even the left-wingers, have serious doubts concerning the wisdom of the Indonesian Government in nationalizing the Bangka Island tin mines, formerly operated by the Dutch Billiton Co. Chief source of American dollars for Indonesia has been the 34,000 ton tin production of its mines. Right now, both left and right are concerned with whether the Government will be able to maintain and increase current production. The right wing Moslem party newspaper, Mimbar Indonesia, stated: "It will no longer be possible any more for radical labor leaders to find foreign scapegoats and tell the workers they are working only for foreign interests and foreign managements. It is up to labor now to increase its labors for the national good. It will be a new experience, and the problem is whether we are capable enough to manage these important mines."

Jan 4, 1953

By AIME AIME

For the convenience of persons who desire to file, or otherwise use separately, the technical papers in Section II of the Bulletin, each of these papers has been paged and wired by itself; the whole collection being held together by a single, heavy wire, upon the removal of which it will fall apart into individual pamphlets, substantially like those formerly issued. A small stock of separate pamphlets, duplicating the technical papers given in Section II of this Bulletin, is reserved for those who desire extra copies of any single paper. All communications concerning the contents of this Bulletin should be addressed to Dr. Joseph Struthers, Assistant Secretary and Editor, 29 W. 39th St., New York City (Telephone number 4600 Bryant).

Jan 1, 1907

By AIME AIME

For the convenience of persons who desire to file, or otherwise use separately, the technical papers in Section II of the Bulletin, each of these papers has been paged and wired by itself; the whole collection being held together by a single, heavy wire, upon the removal of which it will fall apart into individual pamphlets, substantially like those formerly issued. A small stock of separate pamphlets, duplicating the technical papers given in Section II. of this Bulletin, is reserved for those who desire extra copies of any single paper. All communications concerning the contents of this Bulletin should be addressed to Dr. Joseph Struthers, Assistant Secretary and Editor, 99 John St., New York City (P. 0. Box 223; Telephone number 5477 John).

Mar 1, 1906

By E. A. von Hahn, T. R. lngraham

Cementation rates ulere studied by rotating an elec-tropolished or etched copper strip in aqueous solutions, of either perchloric acid or alkaline cyanide, containing silver ions. The rates of cementation were more rapid in acidic media than in cyanide media. In both, the rates varied with the rate of rotation of the copper strip. The deposits formed in the acidic solutions were finely divided, loosely adhering powders. Those formed in the cyanide solutions were dense and adherent. The presence of the deposits influenced the cementation rates. In the acidic solutions the rate was enhanced, possibly because of the increased cathodic area. In the alkaline solutions the rates were decreased in the presence of the deposits. This has been attributed to restricting the diffusion of the copper ion from the rnetal outward into the bulk of the solution. In an earlier paper1 the authors described a kinetic study of the cementation of palladium on copper in perchloric acid solutions. That work indicated that there were two stages in the palladium cementation process. The first, more rapid stage was consistent with rate control by the diffusion of Pd11 ions to the copper surface and/or by chemical reaction at the surface. The second stage was consistent with rate control by the diffusion of copper ions from the copper surface, through the deposit, out into the main body of solution. The effect of the type of deposit on the rate of cementation is of particular interest because it may be one of the primary features involved when large quantities of metal are to be cemented from solution. No substantial investigations of the effect seem to have been made. Accordingly, an extension of the previous work was arranged to study the cementation of silver on copper. This system was selected because of the convenience of the analytical methods, the previously established technology with copper, and the fact that the system could be studied in both acidic and alkaline media. By selecting perchloric acid and alkaline cyanide solutions as the media, it was hoped that some assessment might be made of the effects, on cementation, of having the silver ion present in a virtually uncomplexed state and in a highly complexed state. EXPERIMENTAL The cementation rates were studied, as previously described,' by rotating a copper strip (1.0 by 23.2 cm) clamped to the peripheral surface of a lucite cylinder. The solutions were kept at constant temperatures (±0.05°C) under an atmosphere of purified nitrogen, and samples were taken periodically for analysis. The initial solution volume was 1000 ml and the sample volume 5 ml. The initial silver(1) ion concentrations were made low (0.5 to 1.0 x 10-4 moles per liter) to minimize the influence of the cemented deposit on rates. The solutions were prepared by dilution of suitable aliquots of silver perchlorate and silver cyanide stock solutions. Both stock solutions were prepared from purified silver powder (Johnson, Matthey, and Mallory Ltd.) with redistilled deoxygenated water, and they were kept under an atmosphere of purified nitrogen. To prepare the stock solutions, weighed amounts of silver powder were dissolved with nitric acid. For the AgC104 stock solution the silver nitrate solution was evaporated twice to near dryness with perchloric acid and then made up to volume: For the NaAg(cN)2 stock solution, the silver ions were precipitated with sodium hydroxide solution. The precipitate was filtered, washed thoroughly with redistilled water, dissolved with 1.1 times the required stoichiometric amount of sodium cyanide solution, and made up to volume. The small amounts of free perchloric acid and sodium cyanide present in the stock solutions were disregarded in the preparation of the solutions. The copper strips were cut accurately from 0.025-in. sheet (American Metal Climax OFHC brand) and annealed for 1.5 hr at 470°C in a stream of nitrogen. Analyses of the solution samples for silver and copper were done with a Techtron Model AA-3 atomic absorption spectrophotometer. Calibration standards of the same composition as the experimental solutions were prepared and analyzed simultaneously with the samples. No difficulty was experienced in the analyses, and the reproducibility was within 1 to 2 pct in both alkaline cyanide and perchloric acid solutions.

Jan 1, 1968