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By D. Turnbull, J. E. May

THE (110) [001] texture in silicon iron is of considerable interest both from the technological and scientific points of view. Its occurrence was reported more than 20 years ago.1-4 The texture develops by means of secondary re crystallizatjon5 and can be very strong, that is, greater than 90 pct alignment even thouh the primary re crystallization texture is weak or complex. This behavior is in contradistinction to the face-centered metals which develop their strong secondary recrystalliza-tion texture from a strong primary recrystalliza-tion texture.', The microstructural changes accompanying the (110) [001] texture formation in silicon iron are as follows: When properly prepared cold-rolled sheet (i.e., 0.015 in. thick) is annealed at about 800°C, primary recrystallization occurs and a fairly stable fine-grained primary recrystallized matrix of about 0.02-mm-diam grain size is produced. The material at this stage does not have the strong (110) [110] texture. As the temperature is raised to about 900°C, relatively large grains appear in the finegrained matrix and they grow at the expense of the smaller grains to many times the sheet thickness. In time the complete sample is consumed by these large grains. This process of the growth of relatively few grains (about one in 105 primary grains) at the expense of many grains is called secondary recrystallization. Since all the secondary grains are of essentially (110) [001.] orientation, the strong texture is developed by this secondary recrystallization process. Theories of the (110) [001] texture in polycrystal-line silicon iron have been proposed by Decker and Harker and by Dunn.Decker and Harker have shown that grains initially in the (110) [001] orientation will upon annealing after cold-rolling, re-crystallize back to the initial orientation. To account for the sharp texture in silicon iron they propose that (110) [001] grains become more highly strained than grains in other orientations and therefore recrystallize first. They are then the lowest energy grains and can consume their higher energy neighbors. Grains in orientations other than (110)

Jan 1, 1959

By C. H. Mathewson, P.W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By C. H. Mathewson, P. W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By Robert E. Hoffman, John B. Hudson

The self-diffusion coefficient of pure lead has been measured at five pressures between atmospheric and 40 kb. over a temperature range of about 150°C near the melting point at each pressure. Measurements were made using a radiotracer technique, samples being sectioned electrochemically after the diffusion anneal to determine the diffusion penetration curve. Pressure was applied in a "belt" type pressure device similar to that used by Hall et al., in the diamond synthesis. The self-diffusion coefficient, D, can be represented by an equation of the form at constant pressure, and an equation of the format constant temperature. An apparent correlation between the effects of pressure on self-diffusion and on the melting point of the material observed by Nachtrieb et al., at pressures below 10 kb. was found to be only approximate as measurements are carried to higher pressures. OVER the course of the past 30 years a large number of studies1-' of the rate of atom movements in solid metals have been carried out. These studies have in general been aimed at increasing the understanding of the detailed atomic process by which atom movements in metals can take place. The largest portion of these studies consisted of measurements of the self-diffusion coefficient, D, as a function of temperature. From such studies con- siderable information regarding the energetics of the motive process has been deduced. Recently such measurements have been extended to the pressure dimension. However, the existing work in this area is scanty and has in the past been limited to the pressures attainable in oil or gas bombs—i.e., up to about 10 kilobars (kb). In the present work, the self-diffusion behavior of pure lead has been investigated using the "belt" type high-pressure apparatus designed by Hall7 over a pressure range from atmospheric to 40 kb at temperatures extending over about a 150°C range close to the melting point at each pressure.

Jan 1, 1962

By Waldemar Lindgren, Clyde P. Ross

To the miner, as well as to the geologist, the eastern part of Cuba is a most interesting region. Here we find, in contrast to the moderate relief predominating elsewhere in the island, an imposing mountain range, the Sierra Maestra, extending east and west parallel to the coast, its precipitous front facing the blue Caribbean Sea. In a geological sense this range is largely an unknown land, the only well-explored region being that in the vicinity of Santiago. The range also contains the most important mineral deposits of the island. They comprise, first, a series of iron deposits yielding a partly hematitized magnetite with low content of phosphorus; second, a remarkable copper-bearing vein at El Cobre; and third, various manganese deposits. Probably more deposits will be found, for the larger and western part of the range is as yet little explored and its slopes are covered by a thick tropical jungle. The following notes are based on a short visit by the senior author in January and February of 1914 to the mines at Daiquiri, El Cobre, and Mayari. For many courtesies and great assistance he is deeply obliged to Charles F. Rand, President of the Spanish-American Iron CO.; to George W. Pfeiffer, General Manager, and to the several members of his staff. Geological Features of the Sierra Maestra For our knowledge of the geology of the Sierra Maestra we are indebted to reconnaissance work by Fernandez de Castro, R. T. Hill, Mr. C. Hayes, T. W. Vaughan, and A. C. Spencer. The summary by the latter three geologists furnishes the best guide to the region.' The range is undoubtedly outlined by a great east-west dislocation. Its southern slope drops abruptly to the sea, while on the north side a much gentler declivity leads down to the rolling plateau of Tertiary limestone which occupies much of the adjacent part of the island. Viewed

Jan 1, 1916

FOREWORD A SERIES of papers on strategic and otherwise important mineral products was prepared some ten years ago under the joint auspices of the Committee on Foreign and Domestic Mining Policy of the Mining and Metallurgical Society of America and the Committee on Industrial Preparedness of the American Institute of Mining and Metallurgical Engineers. These papers were later published in a joint volume entitled International Control of Minerals (1925). Amongst them was one on manganese. The Subcommittee on Manganese prepared its paper in two forms. One was intended for inclusion with the series above referred to and approached its subject more particularly as an international problem. The other dealt more definitely with manganese as an element in the problem of national defense. This last was first written under date of January 24, 1924 as a confidential report, for and at the request of the War Department. It was later released and published, in slightly modified form, as a separate pamphlet by the Industrial Preparedness Committee of the American Institute of Mining and Metallurgical Engineers. After the lapse of eight years, in view of the vital position of manga-nese in the problem of industrial preparedness against a war emergency, the War Department made a request to have the conclusions of 1924 reviewed and brought up to date. To comply with this request the manganese subcommittee was reconvened (with a somewhat changed personnel) and exhaustive studies were once more made of the entire subject of manganese. A new report, with specific recommendations, was submitted to the War Department in February, 1932. This second report is now herewith released for publication. Certain specific conclusions and recommendations as expressed to the War Department are omitted. Otherwise the report stands as prepared and submitted by the manganese subcommittee of 1931. The members of this committee were: C. Minot Weld, Chairman, R. C. Allen, Arthur S. Dwight, J. W. Furness, D. F. Hewett, Reno H. Sales, Theodore Swann and Scott Turner. ARTHUR S. DWIGHT, Chairman, Committee on Industrial Preparedness.

Jan 1, 1933

By K. D. McBean, W. H. Hannay, B. A. Stimmel

The electrolytic plant at Trail, B. C., was erected by the Consolidated Mining and Smelting Company of Canada, Ltd., for the treatment of zinc ores and concentrates, particularly those of the Sullivan mine at Kimberley, B. C. It began operations in 1916 at a rated capacity of 60 tons of cathodes per day, which has been steadily increased to the present production of 400 tons per day. The Sullivan has furnished the greater part of the zinc so far produced, although notable tonnages of customs zinc concentrates have been treated. The maximum yearly tonnage of customs concentrates, 25,000 tons, was treated in 1926. Practically no customs concentrates hale been treated since 1929. The total bar zinc production to the close of 1935 was 1,092,782 tons. The zinc mineral in the Sullivan ore is marmatite of somewhat variable composition, ranging between 6ZnS.FeS and 8 ZnS.FeS. Practically all the zinc ores tributary to this plant are marmatites; and the iron content of the zinc mineral varies considerably. The formation of zinc ferrite during roasting is now a matter of common knowledge, so the possible extraction from any zinc concentrate is largely a function of the iron content; the progress made in concentration is reflected directly in zinc-plant recovery. The Trail plant operafes on the low-acid system, as do all the other major plants on this continent at present operating, except the electrolytic plant of the Sullivan Mining Co. at Kellogg, Idaho. The new Magdeburg plant, in Germany, occupies an intermediate position between high and low acid. Plant operation at Trail will be treated in this paper under five main sections: roasting, leaching and purification, electrolysis, cadmium recovery and melting. The oxide section of the plant, treating zinc fume from re-treatment of lead blast-furnace slag, is practically a separate zinc plant; this is necessary because of the presence of fluorine in the smelter zinc fume. Cadmium is recovered electrolytically from the purification residues of both the sulphide and oxide leaching plants.

Jan 1, 1937

A SERIES of papers on strategic and otherwise important mineral products was prepared some ten years ago under the joint auspices of the Committee on Foreign and Domestic Mining Policy of the Mining and Metallurgical Society of America and the Committee on Industrial Preparedness of the American Institute of Mining and Metallurgical. Engineers. These papers were later published in a joint volume entitled International Control of Minerals (1925). Amongst them was one on manganese. The Subcommittee on Manganese prepared its paper in two forms. One was intended for inclusion with the series above referred to and approached its subject more particularly as an international problem. The other dealt more definitely with manganese as an element in the problem of national defense. This last was first written under date of January 24, 1924 as a confidential report, for and at the request of the War Department. It was later released and published, in slightly modified form, as a separate pamphlet by the Industrial Preparedness Committee of the American Institute of Mining and Metallurgical Engineers. After the lapse of eight years, in view of the vital position of manga-nese in the problem of industrial preparedness against a war emergency, the War Department made a request to have the conclusions of 1924 reviewed and brought up to date. To comply with this request the manganese subcommittee was reconvened (with a somewhat changed personnel) and exhaustive studies were once more made of the entire subject of manganese. A new report, with specific recommendations, was submitted to the War Department in February, 1932. This second report is now herewith released for publication. Certain specific conclusions and recommendations as expressed to the War Department are omitted. Otherwise the report stands as prepared and submitted by the manganese subcommittee of 1931. The members of this committee were: C. Minot Weld, Chairman, R. C. Allen, Arthur S. Dwight, J. W. Furness, D. F. Hewett, Reno H. Sales, Theodore Swann and Scott Turner. ARTHUR S. DWIGHT, Chairman, Committee on Industrial Preparedness.

Jan 1, 1933

By Alvinus Brown Wood

THE ancient copper-mines of Lake Superior, having been destroyed or covered by-modern mining-dumps, are not accessible to the present inhabitants of that region, and, since no more are likely to be found, some account of those already discovered, from one who has seen them, may be acceptable to the Institute. Early in May, 1855, 1 took a party of men to open an ancient pit on the Quincy mine-location. Mr. C. C. Douglas was the Agent.," as mine-managers were then called on Lake Superior. The Quincy Co. had previously done work on a fissure-vein, several hundred feet west of the Amygdaloid lode (afterwards called the Pewabic lode), on which was the ancient pit herein described. It was at this pit that the Quincy' main shaft was subsequently stink. The ancient pit showed an apparent depth of about 4 ft., but when cleaned out it was shown to be 14 ft. deep, having been filled up by the sliding-in of material composed largely of broken rock, taken out in sinking the ancient shaft, and left near its mouth. Midway of the shaft, and below water-level, was found a scaffolding, of white-birch poles,- which had been used as a landing, to assist in removing the excavated rock. The shaft was 7 ft. in diameter. The excavation had been done by first building fires in order to disintegrate the rock, as was proved by the abundance of charcoal found; then breaking the softened rock with hammers of diorite, such as is found in the greenstone range on Keweenaw point. These hammers had about. the size of large paving-stones. Only broken ones were found, the whole ones having been doubtless carried away for other work, such as could be traced on the lode for a hundred feet or more to the south. At the place where this shaft was stink, barrel-copper (i.e.,

Mar 1, 1906

A SERIES of papers on strategic and otherwise important mineral products was prepared some ten years ago under the joint auspices of the Committee on Foreign and Domestic Mining Policy of the Mining and Metallurgical Society of America and the Committee on Industrial Preparedness of the American Institute of Mining and Metallurgical Engineers. These papers were later published in a joint volume entitled International Control of Minerals (1925). Amongst them was one on manganese. The Subcommittee on Manganese prepared its paper in two forms. One was intended for inclusion with the series above referred to and approached its subject more particularly as an international problem. The other dealt more definitely with manganese as an element in the problem of national defense. This last was first written under date of January 24, 1924 as a confidential report, for and at the request of the War Department. It was later released and published, in slightly modified form, as a separate pamphlet by the Industrial Preparedness Committee of the American Institute of Mining and Metallurgical Engineers. After the lapse of eight years, in view of the vital position of manga-nese in the problem of industrial preparedness against a war emergency, the War Department made a request to have the conclusions of 1924 reviewed and brought up to date. To comply with this request the manganese subcommittee was reconvened (with a somewhat changed personnel) and exhaustive studies were once more made of the entire subject of manganese. A new report, with specific recommendations, was submitted to the War Department in February, 1932. This second report is now herewith released for publication. Certain specific conclusions and recommendations as expressed to the War Department are omitted. Otherwise the report stands as prepared and submitted by the manganese subcommittee of 1931. The members of this committee were: C. Minot Weld, Chairman, R. C. Allen, Arthur S. Dwight, J. W. Furness, D. F. Hewett, Reno H. Sales, Theodore Swann and Scott Turner. ARTHUR S. DWIGHT, Chairman, Committee on Industrial Preparedness.

Jan 1, 1933

By Charles Burgess

THE improvement, in the quality of cast iron by means of alloy additions has been a metallurgical accomplishment of recent years. Work in this field has shown that chromium is one of the most effective of such additions but, in general, the influence of chromium has been studied only in. connection with other alloying additions, with irons other than foundry irons, or with relatively high percentages of chromium. The present study was initiated for the purpose of determining the influence of small additions of chromium (0.25 to 1.00 per cent) on the quality and resultant properties of cast irons of various foundry grades. The effect of small chromium additions on cast iron was investigated with particular reference to casting characteristics, hardness vs. section, strength, machinability, heat resistance and structure. MATERIAL TESTED Three separate types of cast iron were investigated as to the effect of small chromium additions. The first series of these irons was prepared from remelted foundry cast iron at the Union Carbide and Carbon Research Laboratories, and the other two -series consisted of cupola melts made under usual operating conditions. The first series was made by melting 30-lb. charges of foundry scrap iron containing - 2.86 per cent carbon, 2.72 silicon, 0.50 manganese, 0.062 sulfur and 0.794 phosphorus in a carbon resistance furnace. The chromium was added as high-carbon ferrochrome just before pouring. The irons were cast at approximately 1250° C. (2282° F.). The analysis and physical properties of these irons are given in Table 1, test 1. The second set of cast irons was made in a cupola in accordance with normal practice, 'the charge containing approximately 42 per cent steel scrap and the chromium additions being made to the ladle. Analysis and tests of these heats are shown In Table 1, test 2. A small amount of copper was present in heat C of this series.

Jan 1, 1932

By Philip Davidson, Wm. B. Price

The object of this paper is to present, a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350" C. throughout the coininercial annealing range.. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: Alloy Copper, Lead. Iron. Nickel, ManGanese, Zinc, PeR Cent. Per Cent. Per Cent. Per Cent. Per Cent. PEr Cent. A................ 64.68 Trace 0.194 6.73 0.06 remainder B................ 65.82 1.27 0.227 6.17 0.06 remainder C................ 65.44 Trace 0.345 17.83 0.08 remainder D................ 65.60 1.08 0.238 17.77 0.06 remainder These alloys were lolled in accordance with regular mill practice to approximately No. 6 R. & 6. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 1/2 in. long by 1/2 in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 235 in. were also taken.

Jan 1, 1921

THAT the march of civilization has synchronized with progress in the art of utilizing minerals is a proposition that needs no proof. It is a truism. Historians conveniently divide the time that the earth has been inhabited into the Stone Age, the Bronze (more accurately the Copper) Age, and the Iron Age. As archeologists are not entirely in accord as to dates, and as a few centuries make no difference whatever to this particular story, it may be approximated that the Age of Copper began about 8000 years B.C. and that it gave place to the Age of Iron about 1000 years B.C. The logic of this succession-stone, copper, iron-lies in the fact that copper first displaced stone, then iron displaced copper as the standard material out of which the utensils, implements, and weapons, the utilitarian articles of antiquity, were made. After the advent of iron, the mining and smelting of copper continued. Copper and bronze found use particularly in objects of artistic and ornamental nature; but the superior qualities of iron for many purposes were recognized. Useful manufactures of those days consisted principally of knives, hammers, chisels, spear-heads, arrow-heads, and battle-axes. First these were made of stone, then of copper and bronze, then of iron-particularly as there was plenty of iron ore, and the metallurgy was comparatively easy of accomplishment. Of course, the periods of transition dragged slowly. Definite as were the three Ages dominated by the mineral substance from which they get their names, ten or fifteen centuries probably elapsed from the time the first iron was smelted in a small charcoal furnace until it became the accepted material from which to shape a battle-axe. Contrast this with the pace of modern progress. In a brief span, half a dozen more or less deserving candidates for the distinction of having their name

Jan 1, 1933

By E. A. Barnard

ARSENIC is a very old substance. The ancients speak of it in their writings, and its use has developed very little until recent years. The ancients used it in making pigments, in medicine, and for poison. They also tell of the difficulties of handling it-an experience which is very similar to our own. Until about 10 years ago, arsenic was very cheap and was a drug on the market. About that time the boll weevil began making serious inroads on the American cotton crops, and after much investigation the Depart-ment of Agriculture developed a very successful poison for this pest, consisting of calcium arsenate. The weevil pest has continued, and as the cotton planters have become convinced that calcium arsenate is the best material to use against the weevil, the demands for it have been steadily increasing, resulting not only in a rising price of arsenic but in a very serious shortage so far as our country is concerned. So serious has this shortage become, and so vital is it to the cotton growing industry, that Congress has appointed a committee to investigate and report on the situation. A meeting of arsenic producers and consumers was held in New York last December to take stock of the situation and to see what could be done. The extreme increase in, the market price of arsenic-from 6 c. to 15 c. per lb. in less than a year-has been very harmful to the producers as well as to the consumers. Some very interesting' data were brought out at this meeting, as follows: CONSUMPTION PER YEAR, SHORT TONS Arsenate of lead 2,000 Paris green 1,200 Proprietary mixtures 750 Sheep dips : 1,000 Weed killers 1,500 Glass : 2,000 8,450 1922 Consumption as calcium arsenate 4,000 12,450 1923 Estimated consumption as calcium arsenate... 12,000 Estimated 1923 consumption 20,450

Jan 8, 1923

By William G. Christy

EFFORTS at smoke abatement date back to the year 1273 in England when a law was passed prohibiting the use of "sea cole." The law was not enforced, so King Edward I, 33 years later, appointed a commission "to enquire of all such who burnt sea cole in the city or parts adjoining, and to punish them for first offense with great fines and ransomes, and for the second offense to demolish their furnaces." Many other commissions have since been named to investigate the smoke problem in England, but it still persists in many British cities. In the United States the movement to abate the smoke nuisance started in certain Middle Western cities, and has made considerable progress. Until recently, the coal-producing industry co-operated little in smoke¬abatement programs, taking the attitude that smoke elimination is the dealer's or user's responsibility; and the dealers, in turn placed the responsibility entirely on the user.

Jan 1, 1942

By L. W. McKeehan

The occurrence of twins in large ferrite crystals, made by a new process, was reported in a recent note.' This paper describes a typical case of such twinning and suggests, on the basis of the observed facts, why smooth slip-planes are rarely observed in this metal. Method of Preparation The material in which the crystals here dealt with were grown was made from 1/8in. Armco iron welding rod containing C, 0.04; S, 0.037; P, 0.003; Si, 0.008, and Mn, 0.02 per cent. This rod was cold drawn into wire about 1 mm. dia. A piece of this wire was supported vertically and was locally heated in hydrogen at atmospheric pressure to about 1400" C. by an alternating current (60 cycles per sec.) of about 35 amp., passed through it between a pair of traveling contacts about 8 cm. apart. The rate of travel for the case in hand was 12 cm. per hr. After some 30 cm. of the length of the wire had been heated and cooled in this manner the whole wire was immersed for a few seconds in dilute nitric acid, not restrained by alcohol. Etching was continued until, as nearly as could be judged by eye, the original smooth cylindrical surface of the wire was no longer capable of specular reflection. Measurements The wire in the etched state was next mounted in a goniometer of special form which allowed the measurement of the spherical coordinates of the normals to any plane surfaces left by the etching. These coordinates were most conveniently a polar distance, 8, from one direction of the wire axis, and an azimuth or longitude, ?, from an arbitrary prime meridian. The region to be described more particularly is shown at a low magnification in Fig. 1, which gives two different views, differently illuminated to show the spatial relationship of a crystal occupying most of the part shown and of an inclusion, or rather a series of three inclusions suspected of being twins based on the principal crystal.

By Anson G. Betts

A solution of lead-fluosilicate, containing an excess of fluosilicic acid, has been found to work very satisfactorily as an electrolyte for refining lead. It conducts the current well, iseasily handled and stored, non-volatile and stable under electrolysis, may be made to contain a considerable amount of dissolved lead, and is easily prepared from inexpensive materials. It possesses, however, in common with other lead electrolytes, the defect of yielding a deposit of lead lacking in solidity, which grows in crystalline branches toward the anodes, causing short circuits. But if a reducing-action (practically accomplished by the addition of gelatine or glue) be given to the solution, a perfectly solid and dense deposit is obtained, having very nearly the same structure as electrolytically-deposited copper, and a specific gravity of about 11.36—that of cast-lead. Lead-fluosilicate may be crystallized in very soluble, brilliant crystals, resembling those of lead-nitrate and containing four molecules of water of crystallization, with the formula PbSiF,,4H20. This salt dissolves at 150 C. in 28 per cent. of its weight of water, making a sirupy solution of 2.38 sp. gr. Heated to 60° C., it melts in its water of crystallization. A neutral solution of lead-fluosilicate is partially decomposed on heating, with the formation of a basic insoluble salt and free fluosilicic acid, which keeps the rest of the salt in solution. This decomposition ends when the solution contains, perhaps, 2 per cent. of free acid; and the solution may then be evaporated without further decomposition. The solutioi~s desired for refining are not liable to this decomposition, since they contain much more than 2 per cent. of free acid. The electrical conductivity depends mainly on the acidity of the solution. My first experiments were carried out without the addition of gelatine to the fluosilicate solution. The lead-deposit con-

Jan 1, 1904

By George A. Colligan, John M. Lo

Electrical resistivity as a function of temperature was investigated in undercooled gallium and under-cooled Ga-In alloy of eutectic compositian to examine structural changes in undercooled melts. A continuous linear extension of the resistivity was determined for 99.999 pct pure gallium when undercooled below the stable Ga(l)-liquid, and the metastable Gafl)-liquid equilibria. In icndercooled Ga-In, a significant continuous negative departure from linear resistivity behavior was observed below the eutectic temperature. All resistivity measurements were made by the four-point probe technique. ThE temperature range for investigations into the physical properties of liquids before freezing has been greatly extended with the undercooling of massive melts of pure metals and alloys. Experimental determinations of thermal and transport properties and diffraction patterns in undercooled systems should throw further light on the structural behavior of liquids. Many measurements showing prefreezing anomalies in viscosity1'5 have been regarded677 as evidence for structural groupings in the liquid state. However, the majority of viscosity results,~)~-~~ conforming to the law 17 =A exp(~/RT), do not support theories of atomic aggregation. For the system Cd-Sb, which exhibits a metastable solid phase, Fisher and Phillipsg reported that, in undercooled alloys, the activation energies for viscous flow below the stable liquidus are much higher than those above it. Similarly, Miller et a1." observed a doubling of the activation energies for electrical conductivity in undercooled Cd-ib alloys. These effects were suggested as indicative of atomic association and clustering in the liquids at lower temperatures. With the recent establishment of metastable phases in pure gallium22 and its alloys,23 attempts were made during this investigation to undercool bulk samples and to determine the temperature dependence of electrical resistivitv. Pure gallium, when undercooled below -17°C at atmospheric pressure, can crystallize to either a stable Ga(1) phase (mp, 29.78"C) or a metastable phase identi-

Jan 1, 1967

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half'-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.'' The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By A. E. Nehrenberg

R. A. Schmucker, Jr.—The writer wishes to point out that an acicular growth of austenite, similar to that described in the author's paper, was recently observed in an alloy steel of only 0.06 C content. This steel, which represents an 0.07 max C, 1.35 Cr, 0.55 Ni, 0.20 Mo analysis, combines the characteristics of minimum hardness in the annealed condition with maximum hardenability and is therefore suited primarily for cold-hobbing applications. The acicular austenite formation in this steel was observed accidentally during a determination of its Ac1 temperature. The samples used in this investigation represented as-forged bar stock which had been given a preliminary temper at 1300°F. The critical (Ac1) temperature was finally established at 1400 °F. Fig. 15 represents the microstructure of the sample which had been heated at 1450°F for ½ hr, water quenched, and tempered at 600°F for ½ hr (for the purpose of darkening the martensite). It will be observed from the distribution of the darkened areas of martensite that the parent austenite grains formed at 1450°F had grown in an acicular manner and still occupied only a small percentage of the total area. The remainder of the area contains the original equiaxed ferrite grains in which new austenite had as yet scarcely formed. However, the tiny isolated martensitic patches at several points where three or more ferrite grains intersect indicate that small austenite grains had formed and started to grow in an apparently equiaxed fashion. Fig. 16 represents the prior microstructure of an original sample in the as-forged and tempered condition, before it was heated -above the critical temperature. It is probable that there are two kinds of ferrite in this structure: (1) The equiaxed proeutectoid ferrite grains which separated from the austenite when the steel was cooled from the forging temperature, and (2) the acicular ferrite associated with the aggregate of fine carbide which is represented by the patches of

Jan 1, 1951