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By R. B. Mears, G. F. Sagar, R. H. Brown

There are well recognized procedures for determining the various tensile, fatigue, and other mechanical properties of the common structural materials. This makes it possible for engineers to design structures of various materials which have adequate initial strength to stand the stresses to which they are subjected in service. There is also considerable general information about protective measures suitable for protecting the usual structural materials from the effects of ordinary environments. However, often insufficient quantitative information is available on the combined effects of stress and corrosion to permit the designer satisfactorily to appraise the structure from the stress-corrosion standpoint. This situation is further complicated by the fact that the stresses causing stress¬corrosion failures are usually not the design stresses but rather the residual forming and assembly stresses which are generally of unknown magnitudes. Thus, tests which will rapidly evaluate the susceptibility of materials to stress-cor¬rosion failures are extremely useful. Of particular value are tests which can be applied to built-up structures as well as to simple specimens, since, as mentioned above, residual stresses often are caused by fabricating procedures and assembly operations. The present paper contains

Jan 1, 1945

By AIME AIME

COUNCIL.* PRESIDENT OF THE COUNCIL. CHARLES KIRCHHOFF NEW YORK, N. Y. (Term expires February, 1912.) VICE-PRESIDENTS OF THE COUNCIL. BENJAMIN B. LAWRENCE NEW YORK, N. Y. JOSEPH W. RICHARDS SOUTH BETHLEHEM, PA. ALBERT SAUVEUR CAMBRIDGE, MASS. (Term expires February, 1912.)

Feb 1, 1912

By Valentin R. Garfias, C. O. Isakson

The production of oil in Mexico during 1929 was approximately 45,000,000 bbl., or 5,000,000 bbl. less than in 1928. The production of the fields near Tampico showed a decline of over 10,000,000 bbl. for both the light and heavy crudes, which was partly offset by an increase of over 5,000,000 bbl. in the production of the fields in the Isthmus of Tehuantepec. During 1929 the retrenchment policy followed by practically all the companies was continued and no material improvement should be expected until the unsatisfactory conditions that brought about this situation are remedied. A new administration has just assumed control in Mexico; it should remain in power for 6 years, and the progress of the oil industry during that time will depend primarily on the policy pursued by the new government with respect to oil development. Development During 1929, there were drilled 214 wells as compared with 371 in 1928 and 583 in 1927. The percentage of producers in 1929 was 47.2 as against 34 per cent. in 1928. The new wells did not show water as quickly as in 1928, particularly in the Cacalilao field, where the greatest number of producers was brought in, their average initial daily production being 380 bbl. The flush daily production per well in the Southern fields was 1730 bbl., while the wells in the Isthmus of Tehuantepec came in with an average of 770 bbl. Development is summarized in Table 1. In the Southern fields 63 wells were drilled in 1929, of which 23 were producers, the best being drilled in Paso Real. This development tends to show that the southern extension of Dos Bocas-Alamo fault from Alamo to San Isidro terminates at San Isidro. The two wildcat wells completed in 1929, one in Magiscatzin and the other in Xicotencatl, were failures, and at the end of the year there were eight wildcat wells drilling and material was being hauled for two more.

Jan 1, 1930

By J. C. Bradley

The relation of annealing temperature to conductivity of copper wire has been determined. Conductivity hard was 98.26 per cent. After a 10-min. heat,ing at 200" C. it was 98.69. By annealing 10 min. at 300" C. a large increase, to 100.93, occurred. Maximum conductivity, 101.15, was attained after a 500" C. anneal; thereafter it decreased to 100.53 after a 950" C. anneal. If copper is gassed the decrease is much more than this. Material and Method The work was done on high grade electrolytic copper, 99.942 per cent, copper plus silver, silver 0.0008 per cent. It was hot-rolled to 1/4 in., then cold drawn to 0.080 in. The wire was cut into 25 5-ft. lengths and numbered 1 to 25 as cut. Four samples were tested hard. The others were wound into 5-in. diameter coils. For the 100" C. heating a coil was put into water, the water brought to . boiling, and the wire kept at this temperature for 10 min. For the higher temperatures the coils were placed in envelopes of sheet copper, a little water added, and the envelopes sealed by folding over the edges twice, and hammering them together. This kept the air out very well. The envelope and wire were brought to the desired temperature; this was maintained for 10 min., then the whole was water-quenched. Results Data from the tests are shown in the table and plot (see Fig. 1); conductivity is referred to the International Annealed Copper Standard at 20" C. Conductivity hard is considerably less than conductivity soft.1 The increase is sharp when the wire anneals. The maximum, 101.15 per cent, in the particular material used, comes at 500º C.; thereafter the conductivity falls to 100.53 per cent. after 950" C. annealing, a drop of 0.62 per cent.

Jan 1, 1927

By W. H. Bassett

A 10-year, sea-water, corrosion test of tubes of several copper alloys has shown that many alloys withstood attack by solution, pitting, and dezinkification; a 1-year, salt-spray test of sheet-metal specimens of the same composition showed the same results. THE late J. P. Sparrow, chief operating engineer of the New York Edison Co., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in' September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40, 70-30, 80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.'s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period.

Jan 1, 1925

By W. H. Bassett, C. H. Davis

The late J. P. Sparrow, chief operating engineer of the New York Edison CO., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40,70-30,80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.'s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started on Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period. Plan of Procedure In general, the procedure was to inspect the tubes at short intervals and to remove those that had begun to leak. The tubes removed were carefully examined and a photographic and microscopic record of the

Jan 1, 1925

By John D. Verhoeven, Edward E. Hucke

An experimental technique has been developed for the measurement of the rate of electrotransport to a precision of 1 pct in the molten Bi-Sn system. Results are presented across the phase diagram from 30°C above the liquidus to 520°C. A phenomenological description is presented and the data on Bi-Sn are thereby converted to the effective charge, Analysis of the data indicates the true charge of the migrating tin species in bismuth to be +1.8 at 500°C. The data agree well with the recent work of Belashchmko. fieldintensity. The resistivity of the molten Bi-Sn system is also presented. WHEN an electric field is applied to a metal, a relatively large current is produced due to the ease with which electrons move within the metal. The electric field also produces a force on the ions which might cause them to migrate. Such a migration of metallic ions has been detected under certain conditions. This electromigration of the metallic ions will be referred to herein as electrotransport. The study of electrotransport in metallic systems has a rather long history dating back to the initial work of Gerardin1 in 1861. General reviews of electrotransport in liquid and solid metals have been published by Schwarz,2 Jost,3 Seith,4 and Heumann.5 In reviewing the literature it is apparent that the theoretical developments are not yet complete. The difficulty arises in describing the momentum transfer between the migrating ions and the electrons. In addition, there is a lack of good quantitative electrotransport data at high temperatures, especially in liquid metal systems. This work was undertaken to establish quantitative electrotransport data in a liquid metal system which might serve as a critical test of the theoretical developments. The Bi-Sn system was chosen for analysis, and the rate of electrotransport was determined as a function of temperature and composition. THEORETICAL CONSIDERATIONS If all of the atoms of a metal are considered to be positively charged due to the loss of electrons to the

Jan 1, 1963

By C. S. Barrett

IT has been observed that deformation in iron takes place by slip on {110} + {112} + {123} planes1,2 but in silicon ferrite with low deforma-tion temperatures or high silicon contents (exceeding 4 per cent) the authors have found that slip is confined wholly to {110} planes, at least with small amounts of deformation. The purpose of the present inves-tigation was to determine the effect of this alteration of slip mechanism on preferred orientations in cold-rolled and recrystallized strips. Inci-dental observations on the effect of the recrystallization temperature were also made. The numerous determinations of the texture of cold-rolled iron and steel have been in satisfactory agreement as to the principal features of the texture. (with the exception of a few conclusions that apparently have been based on insufficient data). The texture is chiefly one in which [110] directions of the grains lie along tile direction of rolling, with a deviation of a few degrees, and in which the (100) planes lie in the plane of the rolled sheet, with a deviation from this position chiefly about the rolling direc-tion as all axis 3-9. This deviation about the rolling direction as an axis has been measured by different observers and lies between about 45° and 50° or 60° for iron5,6,9 and is usually in the neighborhood of 50° for mild steel6,7,8. The range of this deviation is a function of the percentage of total reduction 8, 10. Post' reported that it decreases with increasing percentage reduction, but apparently he .studied only the surface material, which Gensamer and Mehl7 found to be somewhat differently oriented from the material in the inside of the sheet. McLachlan and Davey10 found that the deviation also decreases with increasing percentage of total reduction for the material in the interior of the sheet and is independent of the percentage of reduction per pass.

Jan 1, 1937

By Charles Austin

IN an earlier series of studies on 18-8 stainless steel at 600°, 700°, and 800°C.1 one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manu-factured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in, dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0,07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recom-mended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 750°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8 -in. dia., air cooling followed the annealing treatment. These treatments per-mitted two direct comparisons: (1) between the 1150° and 950°C. treat-ments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950° and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By R.J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By R. J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By James Johnston

Synopsis.—A description of the working of the mills of this company and the metallurgical practice in vogue, by which a remarkably complex silver ore, averaging 54 oz. of silver per ton (run-of-mine ore), is treated to give a 95.66 per cent. extraction. The main features of the processes are: The cyanide amalgamation of the high-grade ore. The cyanide treatment of the low-grade ore, after extremely fine grinding and close classification, in a caustic soda solution. The use of a wet desulphurizing process to break up refractory silver minerals. The substitution of aluminum dust for zinc dust as a precipitant. The recovery and shipment of over 13,000,000 oz. of silver in bullion at 997 to 999 fine since this metallurgy was inaugurated, about 2.5 years ago. On the completion and successful operation of the mill to treat their high-grade ore,' the Nipissing Mining Co., under the general management of R. B. Watson, started a series of investigations of the possible treatment of the low-grade ore by the cyanide process, so that they would be in a position to market only silver bullion. These tests were run in July, 1911, on a large scale, by G. H. Clevenger, on an average mixture of Nipissing ore. The results obtained by a partiai amalgamation followed by cyanide treatment gave an extraction varying from 90 to 93 per cent. and were sufficiently encouraging to warrant Charles Butters, the company's Consulting Metallurgist, in recommending that the new low-grade ore mill under contemplation should be a cyanide mill, instead of a concentrator. The cost of such a mill, capable of treating 200 tons per day, to obtain a 90 per cent. extraction at a working cost of $3 per ton of ore treated, was estimated at $250,000. In coming to a decision as to which type of mill should be erected, the concentrator, with the subsequent shipping of concentrates to a smeltery,

Jan 1, 1915

By H. A. Coy, James A. Noble

The Mascot mines of the American Zinc Co. of Tennessee are situated at Mascot, Tenn., 14 miles northeast of Knoxville, on the Southern Railway. The district is centrally located in the Great Valley, or Appalachian Valley Province. Prior to 1900, a small output of zinc was obtained from oxidized ore mined in open pits. In 1900, a shaft was sunk to sulfide ore, and in 1903, a second shaft was put down, neither being as deep as 200 ft. The American Zinc Co. of Tennessee began drilling in 1911, and outlined an ore-body to which its No. 1 shaft was sunk, to a depth of 365 ft. Since that time, the American Zinc Co. of Tennessee has been the only operator in the district. The Federal mining laws have never been in operation in Tennessee and mining lands are as irregular in boundary and area as farm lands. Ownerships are generally held in fee. In most cases the surface and mineral rights are transferred together. Electric power is supplied at 66,000 volts by the Tennessee Power Co., from a hydro-electric plant at Parksville, Polk County, Tenn., 100 miles from Mascot. No other power is used, but an emergency steam plant is held ready in case of interruption of service. Labor is all native and non-union. Negroes are employed for most of the shoveling, and for a few miscellaneous jobs, but for almost no other work. Exploration Exploration is carried ahead of mining largely by surface drilling. Both churn and diamond drills are used. Holes are not spotted according to geometric plan, but to block out ore outlines with the least number of holes. Churn-drill cuttings from each 5-ft. run are mounted for formation record, and in ore ground, all the bailings from each 3 ft. of advance are sampled and assayed. Diamond-drill cores are sampled and a specimen core filed for formation record. In ore ground, all the core

Jan 1, 1925

By J. W. Halley

RIMMING steels derive their name from their action during solidifica-tion in the molds. As a result of incomplete deoxidation, gas is evolved during freezing, and the metal has a characteristic rolling action. The metal rises along the mold walls and descends in the center of the ingot. This action keeps the top of the ingot open and the advancing rim of solid metal can be seen. The rim grows until the rolling action is insufficient to prevent the top of the ingot from freezing or until the action is stopped by capping the ingot with a heavy plate. The violence of the reaction and its characteristics, such as growth or drop ill the molds, are deter-mined by the Composition, the furnace practice, and the deoxidation in the ladle and in the molds. Though rimming steels represent a large proportion of the amount of plain carbon steel made, they have received comparatively little attention in the technical literature. The manufacture of rimming steels has been described by Hibbard,1,2 Fleming,3 Pierce4 and Jackson.5 The reactions occurring during rimming have been considered from the theoretical point of view by Chipman and Samarin.7 The structure of rimmed-steel ingots has been discussed by Nead and one of the present authors.6 Meyer,8 in studying segregation, investigated the distribution of carbon, sulphur and phosphorus in rimmed-steel ingots by analyzing the rim and core of blooms. In their studies of segregation, the Joint Committee of the Iron and Steel Institute and the British Iron and Steel Federations studied distribution in one billet and one ingot of rimmed steel. A detailed study of the distribution throughout the ingot has not been published. The present investigation was undertaken to determine accu-rately the distribution of carbon, manganese and sulphur in normal rimmed ingots and the general distribution of other common elements present. The study included some work on the effect of pouring condi-tions and furnace practice on the distribution, though there is still much to be done in this direction.

Jan 1, 1938

By H. Biloni, G. F. Bolling

The microsegregation in tin specimens containing 0.2, 0.5. or 1 wt pct Pb has been studied m detail. The specimens were grown from the melt in a controlled fashion and exhibited a well-developed cellular substructure. In general, a severe microsegre-gation can be observed in all the photomicrographs presented. Some observations of special interest are: the distribution of a second phase, the presence of a eutectic in several forms, the evidence for dif- THE Smialowski or cellular substructure which forms during solidification has been extensively studied during the past decade.'* Many of the im- *Most references to the cellular substructure except for the last 2 years are reviewed by Winegard.' portant characteristics of this substructure, such as its occurrence and variability with growth conditions, its association with the phenomenon of constitutional supercooling, and its effect on dislocation production and mobility, have received quantitative fusion of solute in the solid, and the enhancement of segregation at a dislocation subboundary network ("striations"). On the basis of the metallographic observations, it can be deduced that the segregation observed is representative of the solute segregation produced during crystal growth. Some deductions are also made about the interplay of the two substructures, cells and striations, and about the mode of cellular growth. investigation both experimentally and theoretically. However, the concentration profile of the solute segregated during crystal growth has not been examined in detail. Tin crystals grown from melts containing various concentrations of lead have been most extensively studied. In a recent investigation of Sn-Pb alloys, Kramer et a1.2 were able to measure the effective solute distribution coefficient, k,, at the most advanced points of the solid-liquid interface, over a large range of growth conditions, finding it to approach the value of k,, the equilibrium distribution coefficient. As will be shown, this must lead to drastic segregation. Another recent study of several Sn-Pb alloys was made by Plaskett and winegard3 who investigated the variation of growth conditions

Jan 1, 1963

By A. B. Cox, L. W. Wark

An attempt has been made to compare the influences of the two most widely used depressants—alkalis and sodium cyanide—and the most widely used activator—copper sulfate—on the air-mineral contact induced by five sulfur-bearing compounds: (1) sodium di-ethyl dithio-phosphate (sodium Aerofloat); (2) potassium ethyl xanthate; (3) sodium di-ethyl dithiocarbamate; (4) potassium iso-amyl xanthate; (5) potassium di-n-amyl dithiocarbamate. Three different organic types are included in lhis group and for two of these types a higher and a lower homologue have been tested. The study of potassium ethyl xanthate, the preliminary results of which have been described,' was continued until there had been obtained a comprehensive account of the influence of variations in pH value and in the concentrations of xanthate, sodium cyanide and copper sulfate on the adsorption of this xanthate by galena, sphalerite, pyrite and chalcopyrite. With concentrations of copper sulfate and collector that the work with ethyl xanthate indicated would give the most illuminating. results, the other four collectors were tested, in a less exhaustive way. The same general principles determine the influence of alkalis, cyanide and copper sulfate, no matter to which type the collector belongs, but there is a gradation in the quantitative measure of such influence. In the list above, the five collectors are cited in the order of their capacity to withstand the depressants, sodium Aerofloat being the least resistant, potassium di-n-amyl dithiocarbamate the most resistant. This order coincides substantially with that of the solubilities of the heavy metal salts formed by double decomposition with the collectors, those formed from sodium Aerofloat being most soluble. There is little difference between the third and fourth members of the series, and under certain conditions their positions are reversed. In general, then, of the three types of collectors investigated, the dithiophosphate type is most easily influenced by depressants, and the

Jan 1, 1935

By G. L. F. Powell

Bulk samples of silver have beat undercooled lo a large degree in contact with crystalline siliceous and ceramic oxide materials, indicating lhat stable oxides and oxide compounds are not the heterogeneous nucleants which normally catalyze cryslallization within a feu degrees of the equilibrium freezing point. Since 400-g samples were undercooled 250°C in contact with cristobalite, it is concluded that the undercooling required for homogeneous nucleation of sil11er is greater than 250°C. Undercooling was Jacilitated by precleaning the crucibles with a high-fires -sure blast of gas. IN numerous experiments on the undercooling of metal melts it has been assumed that a solid glassy surface, being non crystal line, will have no effect in catalyzing crystal nucleation from the melt. Conversely, it is usually accepted that any crystalline surface, in contact with a metal melt, will catalyze nucleation of metal crystals from the melt at degrees of undercooling less than that at which homogeneous nucleation will occur. Both these assumptions were implicit in the claim that homogeneous nucleation was observed in experiments1'2 on the undercooling of small metal droplets (10 to 100 mp diam). The droplets were thought to be freed of suspended crystalline particles which would otherwise catalyze heterogeneous nucleation. They were supported on flakes of silica glass which were assumed to be amorphous, and therefore incapable of acting as substrates for heterogeneous nucleation. In later experiments, large samples of molten metal were undercooled to temperatures similar to those achieved by the droplet technique by melting in a fused-silica crucible3 or a boro-silicate glass slag.4 Since these samples were usually fully enclosed in glass at the moment of freezing, it seemed possible that nucleation was homogeneous when maximum degrees of undercooling were achieved, despite the large size of the samples (up to 500 g). In experiments on the undercooling of silver5 the metal was contained in vitreous silica crucibles, the

Jan 1, 1968

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps: 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the moleculea will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1951