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By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By John V. Beall

Tsumeb has added a chapter to its absorbing history with the beginning of copper smelting operations this month. This development will be followed shortly by another one when lead smelting and refining plants go on the line next year. In our own milieu these events would be common- place enough (although a new lead smelter certainly would be cause for wonder), but in the sparsely settled remote regions of northern South West Africa they are a dramatic industrial expansion. They are also, however, a sound businesslike extension of policies which have marked the tenure of Tsumeb Corp. Ltd. The historical data given in Table I are a drab listing of factual bones without the corporeal splendor which should surround the denouement of the Tsumeb bonanza. When Sir Francis Galton traversed the country, his was an expedition which was in keeping with the then blooming era of heroic explorations. The Otavi highlands in the interior were unexplored and the reception of the natives uncertain. While the exploratory work was in progress during the turn of the century the Hottentots and Hereros were successively in open bloody rebellion. The suppression of these uprisings, particularly the Hereros, by German soldiers so decimated the tribes that a labor shortage ensued for many years, hampering the development of the colony. To these troubles may be added difficulties In obtaining mining supplies. However, there should have been no shortage of meat from wild game judging by conditions prevailing even today.

Jan 12, 1962

By Robert F. Mehl

THE purpose of a symposium, I take it, is to gather together a group interested in a common intellectual field, in order to exchange views, and to appraise the state of knowledge. Symposia are the more successful, the greater the activity in the chosen field and the wider the range of applicability of the information gained. From time to time, as emphasis changes from one field of research to another, a given subject may enjoy popularity and later retire into a scientific somnolence, for fashions change even among engineers and scientists. The subject of this symposium, however, enjoys the advantages of wide applicability and of high current interest and productivity in results. It is a timely subject for a symposium; with much new information, surely metallurgical engineers should now devote an increasing attention to its application to practice. In beginning the symposium, I shall attempt briefly to appraise our basic knowledge in the field, to survey instances of practical usefulness, and to suggest where new work might be most productive of useful results. There are many examples of direct practical application of diffusion knowledge, and it is the purpose of the several papers in this symposium to review these. In this introduction I shall attempt to take a broad view, which, while it will but poorly serve the engineer in the solution of any given problem, may perhaps be of some use in assessing the state of knowledge in this field. RATE OF DIFFUSION Liquid Metals The process of diffusion among liquid metals, of gases in liquid or solid metals, or among solid metals, is ubiquitous, to say the least. The manufacture of alloys by the intermelting of metals, the addition of ferroalloys to molten steel, the deoxidation of molten alloys, all involve diffusion in the liquid state. The oxidation of molten copper for purposes of purification, the unsought oxidation of alloys generally during melting and casting, the reaction of liquid steel with oxidizing slags in the open-hearth furnace, the absorption of nitrogen by liquid steel, particularly in the bessemer furnace, all operate by the diffusion of gases in liquid metals. These processes have not been studied much from the viewpoint of rates of diffusion. Alloys are made by melting metals with stirring and with allowance of time for mixing (which is diffusion) but I know of no studies that seem to define the necessary times, and though in only very rare cases can faulty properties of the finished castings be ascribed to inadequate mixing, and though certainly in most cases, with stirring, the rate of diffusion is adequate to give sufficient mixing, a more quantitative treatment would be good to have. It is not wholly certain that thorough and sufficient mixing is at all times attained, for I suspect that ferroalloy additions to steel, and that additions of aluminum to steel as a deoxidizer, especially in the sampling of steels

Jan 1, 1944

By William E. Greenawalt

Ever since electrolytic copper refining gave promise of success, about a half century ago, efforts have been made to apply the idea to the extraction of copper from its ores. The methods of attack have, usually, been to leach with a dilute acid and then to deposit electrolytically the copper from the resulting solution with the simultaneous regeneration of the solvent used in the process. Many efforts have been made, and many patents have been taken out, both in the United States and abroad, to give this idea practical application, but only within the past few years have the difficulties been surmounted. Leaching and electrolysis, as applied to copper ores, are among the most promising fields in modern metallurgy. New conditions are arising, which will bring the wet methods into prominence; while high freight rates and increasing cost of fuel will tend to limit smelting to highly favored localities. The possibilities offered by the installation of hydroelectric plants and the greatly enlarged range of power transmission will greatly widen the field of electrolytic methods. Electrolytic methods are ideally adapted to hydroelectric development, for the load is constant throughout the full twenty-four hours, and the cost of both installation and operation of hydroelectric plants is not appreciably greater when operating for twenty-four hours than when operating for eight or ten hours; whereas, in fuel-power generation, as also in smelting, the cost is more or less in proportion to the fuel and power used. Nevertheless, fuel-power generation presents advantages in electrolytic methods, as the power plant may be located in a favorable place while the leaching and electrolytic plants may be located at the mine. The ultimate possibilities of the wet methods have yet to be determined. The possibilities of smelting have been thoroughly worked out; there is no unsolved major problem in copper smelting, and it has practically reached the limit of its possibilities. It seems hardly probable that any future improvement, either of method or apparatus, will greatly

Jan 1, 1924

By B. F. Bush

THE coal-fields of Missouri, situated hi the northern and western portion of the State, are distributed, in whole or in part, over 57 counties, embracing an area estimated by Mr. Broad-head to be practically 23,000 sq. miles, including small detached beds and outliers in St. Louis, St. Charles, Lincoln and Warren counties in the eastern part of the State. This area includes about 8,000 sq. miles of Upper or Barren Measures, 2,000 sq. miles of exposed Middle, and 12,420 sq. miles of exposed Lower Measures. In a general way, the Missouri coal-field is bounded on the east by an imaginary line entering the northern part of the State just east of the 92c1 Meridian and passing across the State in a southwesterly direction to a point on the Kansas-Missouri line a little below the southern boundary of Barton county. An important part of the field overlaps this line and extends down the northern side of the Missouri river, under¬lying the greater part of Randolph, Howard, Boone and Audrain counties. In all, 34 counties produced coal during the year 1903. Fig. 1 shows the position of the coal-fields in Missouri. GEOLOGICAL FEATURES. The Coal Measure formations, all of the Carboniferous age, rest unconformably upon the rocks of the sub-Carboniferous or Mississippian series, and, in some cases, upon the rocks of the Devonian and Silurian ages. From their outcrop on the eastern and southeastern borders of the field, the Measures dip west to northwest at the rate of 10 ft. per mile, reaching a maximum thickness estimated by

Jan 1, 1905

By Max C. Eastman, V. H. Wilhelm

California had a record year in production and drilling activity, but the results have not been sufficient to keep up with the enormous increase in demand due to war activity. During the year, 164 dry wildcats were drilled, 80 dry wells in proved areas, 31 gas wells, and 1158 successful oil-well completions for a total of 1433 wells, compared with a total of 765 in 1942. With new discoveries of only 20,000,000 and production of 283,000,000 bbl. for the year, total reserves of California oil have decreased more than 250,000,000 bbl. However, revised estimates of the reserves of old fields indicate an increase in the state's reserves of I00,000,000 barrels. The completion of 1158 wells has served only to maintain the maximum efficient daily rate of production at 800,000 barrels. There is evidence in many fields that oil is being withdrawn too rapidly to obtain the maximum recovery, and more rapidly than is conducive to good production practice. Statistics for 1943 as compared with I942 are shown in the table in the next column, Supply and Demand Steadily mounting needs of the military forces and increased industrial consumption raised total demand for all petroleum products on the Pacific Coast to 914,000 bbl. daily in 1943. That all-time record demand was 149,ooo bbl. daily higher than in 1942 and 214,000 bbl. daily above 1941 demand. Despite restrictions due to shortages of critical material, crude-oil production was boosted from 680,000 bbl. daily in 1942 to 779,000 bbl. daily in 1943, the highest level in 15 years. However, the new crude supply plus natural gasoline production and imports from other states totaled only 840,000 bbl. daily, leaving a deficiency between supply and demand of 74,000 bbl. daily. That shortage had to be made up by withdrawals from inventories, which had been steadily depleted during the previous four years. Aboveground reserves, which totaled 159,574,000 bbl. on Jan. I, 1939, were down to ~8.000,000, bbl. at the end of 1943. Significantly enough, the greater part of that decrease occurred during the last six months of I9437 when more than 23,000,000 bbl. was taken from inventories of both crude and products. Although the size of total inventories on Dec. 31, 1943 might appear substantial, about 65 per

Jan 1, 1944

By Max C. Eastman, V. H. Wilhelm

California had a record year in production and drilling activity, but the results have not been sufficient to keep up with the enormous increase in demand due to war activity. During the year, 164 dry wildcats were drilled, 80 dry wells in proved areas, 31 gas wells, and 1158 successful oil-well completions for a total of 1433 wells, compared with a total of 765 in 1942. With new discoveries of only 20,000,000 and production of 283,000,000 bbl. for the year, total reserves of California oil have decreased more than 250,000,000 bbl. However, revised estimates of the reserves of old fields indicate an increase in the state's reserves of I00,000,000 barrels. The completion of 1158 wells has served only to maintain the maximum efficient daily rate of production at 800,000 barrels. There is evidence in many fields that oil is being withdrawn too rapidly to obtain the maximum recovery, and more rapidly than is conducive to good production practice. Statistics for 1943 as compared with I942 are shown in the table in the next column, Supply and Demand Steadily mounting needs of the military forces and increased industrial consumption raised total demand for all petroleum products on the Pacific Coast to 914,000 bbl. daily in 1943. That all-time record demand was 149,ooo bbl. daily higher than in 1942 and 214,000 bbl. daily above 1941 demand. Despite restrictions due to shortages of critical material, crude-oil production was boosted from 680,000 bbl. daily in 1942 to 779,000 bbl. daily in 1943, the highest level in 15 years. However, the new crude supply plus natural gasoline production and imports from other states totaled only 840,000 bbl. daily, leaving a deficiency between supply and demand of 74,000 bbl. daily. That shortage had to be made up by withdrawals from inventories, which had been steadily depleted during the previous four years. Aboveground reserves, which totaled 159,574,000 bbl. on Jan. I, 1939, were down to ~8.000,000, bbl. at the end of 1943. Significantly enough, the greater part of that decrease occurred during the last six months of I9437 when more than 23,000,000 bbl. was taken from inventories of both crude and products. Although the size of total inventories on Dec. 31, 1943 might appear substantial, about 65 per

Jan 1, 1944

By E. P. Mathewson

THE OLD Pueblo smelter is being dismantled after 43 years of continuous operation, from 1878 to 1921. It was built by Mather and Geist, on a bluff overlooking the Arkansas River just below the, city of Pueblo. At the time of its construction Pueblo was considered a most favorably situated town for a custom smelter. Coal, coke, fuel, limestone, iron ore, lead, silver, and, gold ores were plentiful. It was a "downhill pull" from all directions to Pueblo. Labor, both common and skilled, was plentiful and efficient. Leadville was in bonanza and there were not sufficient furnaces in Colorado to handle the ore offered. The plant prospered from the start. It soon required more capital; so the owners; with the assistance of Thomas Nickerson of Boston, at that time prominent in the affairs of the A., T. & S. F. railway, formed the Pueblo Smelting & Refining Co. About this time, also, very heavy shipments of rich silver ore from New Mexico began to come in. Agencies were established for the purchase of ores in the most important mining camps in the country from Kingman, Ariz., to Butte, Mont. Highly siliceous silver-bearing ores from Butte were shipped to Pueblo in train loads. This was used chiefly in the concentration of leady mattes. RECOLLECTIONS OF MR. GEIST, FOUNDER OF PLANT Mr. Geist is living in Guadalajara and has sent the following brief letter: "Early in 1878 the firm of Mather & Geist, which had been operating in Utah and had then closed their smelter there, after diligent search for a new location selected Pueblo. We erected the first smelter in the valley, blowing in the first furnace in 1878. Mather & Geist carried on until January, 1882, when they transferred all their business to the Pueblo Smelting & Refining Co., which had been organized in December, 1881. Full details of this transfer are given in the enclosed Report, which was issued early in 1882, for the purpose of interesting more capital, in which we succeeded admirably. "I personally did all the work of manager and super-intendent, some job in these days. My technical quali-fications were that I was a member of the class of 1866, Yale Sheffield Scientific. I was born in 1848, so was the youngest member of the class.

Jan 11, 1923

By Joseph W. Roe

MANY questions arising in the work of the mining engineer may be solved quickly and with sufficient accuracy by the methods of descriptive geometry; but, unfortunately, this subject is more often considered from a mathematical view-point than as an effective tool. for solving practical problems. Some of the principles involved are merged into the ordinary operations of mechanical drawing, and are used unconsciously by the engineer in his every-day work. The rest are stowed away on the book-shelf with his forgotten or rarely-used college text-books. One reason for this condition of "innocuous desuetude " may lie in the unfortunate and often cumbersome notation which it has been found necessary to introduce. If some of these principles can be recalled to the engineer's attention in terms of every-day use they may prove of practical bearing. Recently, in talking with several mining engineers, I used some of the drawing-room methods of a machine-designer, to the evident surprise of those around me. These men were perfectly familiar with the methods, but their application to mining-work had not occurred to them. At their suggestion the present paper is offered, not in any way as a treatise, but merely to suggest a certain point of view, in hope that it may lead others far more familiar with mining-problems to pursue the subject further. I. To FIND THE STRIKE. As the simplest and most fundamental problem, let it be required to find the strike of a vein when the location and elevation of three points on the outcrop are known. It will be assumed for the present that the vein is a plane.

Mar 1, 1910

By James A. Barr

Phosphate rock is a natural rock containing one or more phosphate minerals usually calcium phosphate, of sufficient purity and quantity to permit its use, either directly or after beneficiation in the manufacture of commercial products.1 The principal minerals in phosphate rock have the apatite structure which may be represented by the type formula: Ca10(X2) (PO4)6 where X represents the hydroxyl group (OH), chlorine or fluorine, either singly or collectively. The calcium may be partly replaced by sodium, magnesium, and other positive ions such as manganese, strontium, lead, uranium, cerium, yttrium and other rare earths. The PO4 radical may be partly replaced by small quantities of UO4, AsO4, SiO4, CO3, SO4, or Vo4. A typical commercial rock is usually a calcium phosphate containing 3 to 4 pct fluorine, the major impurities being limonite or other iron oxides, clay, aluminum phosphates and silica as quartz sand. A little vanadium is present in most of the domestic rock deposits (except the Tennessee Brown Rock), according to Jacob, Hill, Marshall and Reynolds! A little uranium occurs in the Florida leached zone, as will be brought out later. The chemical analyses are reported as P205, or tricalcium phosphate Ca3(PO4)2, the latter often designated by the trade name BPL (bone phosphate of lime). Commercial analyses usually report iron and alumina as oxides, lime as CaO and silica or insoluble. Colony3 examined many samples of apatite, staffelite, dahlite and American phosphorites and concluded that all have identical X-ray diffraction patterns. The phosphates in the phosphate rock have very minute crystalline structures. The mineral apatite Ca3(F.Cl) (PO4) 3 is the principal primary source of the element phosphorus, and occurs widely distributed in igneous rocks but rarely in a minable mass. Only about 12 pct of the world production of phosphate rock comes from primary apatites; the remainder is derived from secondary phosphorites. These phosphorites have been formed by the alteration of sediments by solutions containing phosphoric acid. Such solutions have come from the weathering or leaching of igneous rock containing apatite, bone deposits of prehistoric animals, marine life or guano deposits. These phosphorites are mostly alterations of phosphatic limestones. The sedimentary phosphate deposits are of marine origin and may have been enriched by subsequent solution of the more soluble calcium carbonate by waters containing carbon dioxide, by physical concentration by wave action, and by redeposition of the dissolved phosphate ions. Uses of Phosphate Phosphorus is the spark of life and is the structure builder and one of the main elements of plant food (fertilizer). Without phosphorus, life cannot exist. A "complete" plant food[t] in addition to phosphorus compounds contains potash, which acts as a catalyst to convert nutrients to useful forms, nitrogen to supply the growth element and many minor elements. The cycle of supply of phosphorus is from the apatite to solution and soil, absorption of plant life, decay and return to the soil or by animal life feeding on the plants. With insufficient supply of phosphorus in vegetation, life is not prolific. If crops are removed from

Jan 1, 1960

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964

By R. E. Miner, J. K. Jackson, D. F. Gibbons

Internal-friction measurements were made during isothermal aging treatments of 18 pct Ni maraging-steel wires between 420° and 612°C. A sharp initial drop in the internal-friction level was interpreted in terms of a rapid dislocation recovery reaction. The rate of the recovery was found to be independent of temperature. Truncation of the recovery reaction was apparent in those systems that exhibited the rapid age-hardening characteristics of the maraging steels. It is proposed that this initial hardening response is the result of a low activation energy preprecipitation reaction involving molybdenum. A gradual rise in the internal-friction level at longer aging times was associated with the precipitation of a molybdenum-containing precipitate. CONSIDERABLE research effort has recently been devoted to the mechanisms responsible for the high strength and toughness of 18 pct Ni maraging steels. These bcc martensitic alloys are found to harden during aging at temperatures between 400° and 600°C. The aging response is very rapid with more than half the total hardness increase occurring within the first few minutes of aging, Fig. 1. Precipitate particles have been observed in the later stages of aging by a number of investigators.&apos;-&apos; While the identity of the precipitates remains the subject of some controversy, one or more of the intermetallic compounds, Ni3Mo, Ni3Ti, and Fe2Mo, are almost certainly involved. Heterogeneous nucleation of precipitates at dislocations has been noted8 and cobalt is believed to enhance the formation of fine, homogeneously distributed particles by lowering the solubility of the alloying elements in the martensitic matrix.3,7 Transmission electron microscopy studies of the initial hardening behavior have not been fruitful. Strengthening mechanisms based on atomic ordering have not been generally supported by X-ray and neutron-diffraction experiments.9 In the present investigation, the aging reaction was studied using isothermal-aging internal-friction measurements. The marked sensitivity of internal friction to short-range diffusion and precipitation processes has provided a convenient tool for the elucidation of the strengthening mechanisms operative in the maraging steels. EXPERIMENTAL PROCEDURE An upright torsion pendulum was used to measure the internal friction of several maraging steels during isothermal aging. The pendulum was placed in an atmosphere of helium at a pressure slightly less than atmospheric. To permit measurement of internal friction during the first minutes of aging, the specimens were rapidly heated by passing a current through them in a manner similar to that described by Ang and Wert.10 Thermal gradients in the specimen were largely eliminated by using specially designed specimen grips11 which produced temperature variations of less than 1 pct over 90 pct of the specimen length and less than 3 pct over the entire length at aging temperatures up to 620°C. A proportioning strip-chart program controller was employed to maintain constant specimen temperature during treatments of up to 36 hr duration. A number of vacuum-melted laboratory heats having compositions near that of a typical commercial 18Ni-7Co-5Mo-0.4Ti alloy were investigated. The amount of cobalt was varied from 0 to 7 wt pct in five of the heats. Either molybdenum or titanium was omitted in the remaining two heats. The alloy desig-

Jan 1, 1967

By C. J. Sparks, J. C. Ogle, E. A. Starke

DEFORMATION of cold-rolled fcc metals and alloys produces one or the other of two types of rolling textures, usually referred to as the copper type or the brass type. The pure fcc metals, with the exception of silver, develop the copper-type texture when rolled at room temperature. Silver, brass, and many other alloys develop the brass-type texture. Transition from one texture type to another can also occur. Solute additions to pure copper cause a transition from the copper-type to the brass-type texture.&apos; Varying the deformation temperature also produces texture transitions. Copper rolled at -196°C developed the brass-type texture2 and silver rolled at elevated temperatures, 200°C, developed the copper-type texture.374 The work of Haessner,&apos; Smallman and Green,6 and Hu and coworkers3&apos;4 seems to have established an apparent correlation between the type of rolling texture (and the texture transition) and the stacking-fault probability. Thus materials with low stacking-fault energies are thought to develop the brass-type texture while high stacking-fault energy materials develop the copper-type texture. Mikkola and cohen7 measured by X-ray diffraction techniques the stacking-fault probability, a, in the ordered and disordered fcc alloy Cu3Au. Unexpectedly, ordered specimens showed about twice the stacking-fault probability as the disordered ones. Marcinkowski and Zwe118 also found stacking faults in ordered Cu,Au, but not in the disordered CusAu. More recently, Camanzi and coworkers9 have shown that the intrinsic stacking-fault energy of Cu3Au undergoes a considerable decrease (approximately 100 ergs per sq cm) when passing from the disordered to the ordered phase. In general, deformation reduces order&apos;&apos; but some of our measurements showed that some long-range order still remains in Cu3Au after cold reduction by rolling 80 pct. From the above considerations Cu3Au offers the possibility of studying the texture transition in fcc alloys without varying either the temperature or the composition. If the stacking-fault energy correlation is correct, an initially ordered alloy should develop the brass-type texture during rolling while a disordered alloy should develop the copper-type texture. The present communication describes some initial results of experiments designed to investigate this possibility. The rolling textures of ordered and disordered Cu3Au samples were determined after various amounts of deformation. The ordered sample had an initial long-range-order parameter of S = 1, determined from X-ray diffraction. The grain size of both the ordered and disordered samples was the same, and the initial textures of both were also identical and approximately random. No obvious differences in the deformation textures of the ordered and disordered materials were detected up to 35 pct reduction and the (111) pole figures of Fig. 1 resemble that of pure copper. However, with reduction larger than 35 pct and less than 50 pct, a marked deviation from the copper texture was noted in the ordered material. The newly developed orientation was close to the (110)[i12] ideal orientations re-

Jan 1, 1970

By Victor O. Homerberg, Dexter N. Shaw

A study of the correlation of the mechanical properties and of the microstructure with the heat treatment of 60-40 brass has been confined, heretofore, to the rolled or extruded material as received from the mannfacturer. The results obtained by Babson and Buhler,&apos; Bengough and Hudson12 Stead and Stedman,3 and Brayton4 have been confined to the treatment of the material as received. No attempt was made to get the material into a given condition and then to work from this basis. To start with a given structure would have the decided advantage of making the work independent of the original condition, hence, to make the results reproduceable. In a previous paper, it was shown, in connection with the study of the transformation that occurs at about 470" C., that if specimens were quenched to produce the beta structure and then reheated, the beta would begin to break down, at approximately 200" C., into a very finely divided alpha. It was predicted that important results might be obtained if test pieces were to be given a similar double heat treatment and then tested for the mechanical properties as well as a study of the microstructure. The material used in the present investigation was a 3/4-in. round bar of extruded muntz metal of the following composition: Copper, 61.05 per cent.; zinc (by difference), 38.90 per cent.; lead, 0.05 per cent.; iron, trace; tin, nil.

Jan 1, 1924

By M. A. Dayananda, R. E. Grace, P. F. Kirsch

Ternary diffusion experiments were carried out at 750°C with vapor-solid diffusion couples in single-phase copper-rich Cu-Zn-Sn alloys. The Philibert-Guy method was used to calculate intrinsic diffusion coefficients at compositions corresponding to the plane of inert markers imbedded in the diffusion couples. Inter diffusion coefficients were determined at common composition points of intersecting diffusion paths. Intevdiffusion coefficients were also obtained at compositions corresponding to maxima in the tin concentration pvofiles Relations between the interdiffusion coefficients and the expansion of vapor-solid diffusion couples are described in detail. Such relations permit the calculation of constant interdiffusion coefficients in binary couples from expansion data directly. In ternary couples expansion data provide an additional constraint on the interdiffusion coefficzents. ThE phenomenological analysis of diffusion in ternary solid solutions has been developed extensively, and various approaches taken in the determination of diffusion coefficients have been reviewed recently by Guy et al.&apos; Finite,&apos; semi-infinite,3 and infinite4 diffusion couples have been used in studies of ternary diffusion, but most of the work has been done with infinite diffusion couples. Semi-infinite diffusion couples3 (vapor-solid couples) have been used to determine both intrinsic and interdiffusion coefficients in the Cu-Zn-Mn system, in which two diffusing species, zinc and manganese, were supplied from the vapor phase. If only one component has a sufficiently high vapor pressure to be supplied from a vapor source, vapor-solid diffusion couples may still be used. In this case the boundary conditions at the gas/solid interface may be governed by partial equilibria rather than by virtually complete equilibrium between the phases. In the present work diffusion measurements were carried out at 750°C with vapor-solid couples of Cu-Zn-Sn alloys. Only zinc was transported between the vapor source and the diffusion disks, because the vapor pressures of both copper and tin are at least 108 lower than that of zinc. Both intrinsic and interdiffusion measurements were made at several compositions. A secondary objective was to relate expansion of the diffusion couples with the interdiffusion process. Such measurements for binary couples yield average values of the interdiffusion coefficients over composition increments. In ternary diffusion couples ex- pansion data provide an additional constraint on the interdiffusion coefficients. COMPOSITION-DEPENDENT INTRINSIC AND INTERDIFFUSION COEFFICIENTS As shown by Philibert and GUy5 the determination of intrinsic diffusion coefficients in a ternary system requires two independent diffusion couples containing marker planes with identical composition. In the case of vapor-solid couples such a requirement torresponds to two couples set up with the same vapor source exposed to two diffusion disks of different composition. Inert markers placed initially on the disk surfaces become imbedded during diffusion. If the pair of couples exhibits appreciable marker burial with marker planes of virtually the same composition, the intrinsic diffusion coefficient may be evaluated at the composition of the marker planes. Fig. 1 is a schematic diagram of the concentration of of a Cu-Zn-Sn ternary vapor-solid couple after diffusion of zinc from a vapor source into a binary Cu-Sn alloy. The areas, Ai correspond to the cumulative intrinsic fluxes of the three diffusing species across the marker plane:5 where Ji is the intrinsic flux of component i, t is the diffusion time, and D3i are the intrinsic diffusion coefficients. For the determination of interdiffusion coefficients a pair of diffusion couples with intersecting diffusion paths is needed. At the composition point of intersection (C1, C2) the coefficients are evaluated from the equation:3

Jan 1, 1969

By W. Shockley

THIS lecture can best begin with a statement of the chief conclusion: The metallurgical industry will find profit in supporting fundamental research on dislocations. This support should be done both in their own laboratories and in universities. My lecture consists of an exposition of the basis for this conclusion. The experience on which I base it is drawn largely from two fields in solid state physics—one field is transistor electronics and the other is dislocation theory. At present the relationship of solid state physics to technology is different in these two fields. In electronics without question, the physics has led the technology. In metallurgy, on the other hand, the technology in the form of metallurgical art is far ahead of the fundamental science. In transistor electronics, physics has suggested and can still suggest previously unachieved combinations of matter that will have new and useful properties; that is, the physicist can make specific predictions. The physicist can also have some confidence that the predicted devices will actually come into existence in a matter of months or years and that they will live up to the predictions. In metallurgy, the physicist cannot to a comparable degree make predictions and have the same hope that they will lead to something new and valuable. There are a number of reasons for this difference. The first is simply historical. Transistor physics is young. It may be regarded as dating from the announcement of the transistor, in which case it is about four years old, or from the first real control of semiconductors as materials (this was accomplished largely by metallurgists, by the way) in which case it is about ten years old. Metallurgical art, on the other hand, is thousands of years old. There is no doubt that the advance of this art has been and will be hastened by a good fundamental understanding of the quantum theory of atomic phenomena. It, is too much to expect, however, that theory will soon catch up with the lead that practice has gained in a thousand years, and that theory will then point out specific pathways to better materials. It seems more probable that modern atomic theory will serve to interpret and organize information much as thermodynamics has done through phase diagrams. In this lecture, I shall emphasize an important feature common to both solid state electronics and to metallurgy. This common feature is the harmonizing principle that justifies discussing electronics and metallurgy as related topics in solid state physics. In both cases the important properties of the materials arise from imperfections. By imper- fections I mean deviations of the materials from perfect single crystals. The imperfections may be of many forms. From the point of view of utility they may be either good or bad, and a given type may be good or bad depending on circumstances. The technical material of my lecture will be divided into two parts. The first will be chiefly concerned with four types of imperfections in germanium crystals. The control of these imperfections makes possible the fabrication of useful electronic devices. A good example of such control is the junction transistor, which I shall discuss from this viewpoint later. The junction transistor, as some of you may have heard, can be used as an amplifier of electrical signals and in a number of respects surpasses what has hitherto been achieved with vacuum tubes. The second part of my technical material will be concerned with dislocations. For about fifteen years the theoretical physicist has had dislocations in mind as the most important kind of imperfection in metals. He has, however, until recently had experimental material of a highly speculative nature to back up his assertions. I am fortunate in the timing of this lecture to be able to describe some recent results that put dislocations on a far more definite basis than has been the case in the past. In fact there are now some experiments which reveal the characteristic properties of dislocations almost as clearly as experiments in transistor physics reveal the properties of holes and electrons, properties that I shall soon describe. It is this advance in the status of dislocations that emboldened me to make my initial assertion that the metallurgical industry will profit from supporting fundamental research on dislocations. Transistor Electronics In order to discuss imperfections in semiconductors, it is necessary to visualize a reference condition that may be regarded as perfect. In the cases of silicon and germanium, which find application in transistor electronics,&apos; the perfect structure is the diamond structure shown in Fig. I. In this structure, each atom is surrounded by four neighbors with which it forms four covalent or electron-pair bonds. These bonds use all of the four valence electrons possessed by each of the silicon or germanium atoms. The electronic structure of the crystal is thus complete and perfect. A crystal of silicon or germanium with a perfect electron-pair bond structure would be an insulator, In order for electrical conduction to occur, it is necessary for imperfections to arise in the electronic structure. In this lecture, I shall discuss four possible imperfections whose symbols and relationships are indicated in Table I. We shall consider first, as an example, a crystal of silicon containing an arsenic atom as an impurity.

Jan 1, 1953

By J. J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. ALTHOUGH the production of aluminum is a large-scale industrial process, consuming approximately 3 pet of all of the electric current generated in this country, the mechanism of the Hall Process remains a 70-year-old mystery. It is a remarkable fact that the aluminum industry, which was established largely through research and owes much of its growth to research, still employs as its basic process the one developed by Charles Martin Hall while he was still a young man working in a woodshed. There are, of course, modifications in detail and a tremendous expansion of the size of the units used, but basically the process employs carbon anodes and a carbon-lined iron vessel as a cathode for the electrolysis of alumina dissolved in molten salt. Of the almost infinite variety of salts available, the relatively minor Greenland mineral, cryolite, 3NaF.A1F3, is still the only one which gives good performance in the electrolysis. In the early days, the process was thought of as a simple one. The dissolved alumina dissociated and, during the electrolysis, the aluminum was carried to the cathode where it was discharged and collected in a pool of metal. The oxygen was carried to the carbon anode where it reacted to form primarily carbon dioxide together with some carbon monoxide. About the only virtue that can be claimed for this hypothesis is that of simplicity. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. The complexity of the literature on this system is demonstrated in Table I, which shows the ions postulated as being present during the process. This system is not easy to investigate. Cryolite melts at about 1000°C, so that all the investigations are at relatively high temperatures. Molten cryolite fumes in air, particularly if excess aluminum fluoride is present. The cryolite changes composition on heating at 1000°C, principally by reaction with moisture in the air, but apparently also by reaction with oxygen. Cryolite reacts with most of the customary materials of construction, and those that are not attacked by cryolite seem inevitably to react with molten aluminum. Graphite is the only common material that is inert to the electrolytic bath. Pure cryolite can be held in platinum. There is hope that some of the newer refractories will stand up in bath, and their development for this purpose would be a major advance in the field. The techniques to be discussed, then, are not the most advanced ones. Rather, they are examples of old standardized methods applied under difficult conditions. The principal methods that shed real light on the mechanism are density, electrical conductivity, freezing-point lowering, transport number, viscosity measurements, and reactivity of bath with carbon dioxide. The first measurement to be discussed is density. This procedure is relatively straightforward. A hollow platinum bob is suspended by fine platinum wire from an analytical balance into the melt being investigated. Density1-4 of the system sodium fluoride-aluminum fluoride is shown in Fig. 1. There is a maximum in the density near the cryolite composition, but actually the maximum is on the NaF-rich side of cryolite, close to the composition NaF - Na3AlF8. Density measurements are also useful in giving a clue to the nature of cryolite-alumina melts.1, 4 On the first addition of alumina, density decreases, Fig. 2, although the density of alumina, either solid or liquid, is higher than that of cryolite. These density results indicate that the systems are not simple. A great deal of effort has been spent in measuring the electrical conductivity of molten cryolite and of cryolite with various additives. Conductivity measurements are quite easy for fused salts that can be measured in a dip cell, but no successful dip cell has been made available yet for cryolite. Recourse is had

Jan 1, 1959

By F. C. Miller

The metallurgical fuel of Colorado, Utah, and New Mexico has been a Veiny tardy member in the caravan of western industrial progress. The history of western coke has naturally been closely related to the development of the metallurgy of iron and steel and the precious metals, in the State of Colorado. It was at Leadville, with a population of 300 in 1877, that the Sentinel was published by Richard S. Allen. The Sentinel gave very full accounts of the various mineral discoveries at the new town of Leadville, which found their way to the more widely circulated journals of the East, and attracted the attention of many people. At the close of 1878, a census slowed a total of 5040 persons. The first smelter was established in 1877, at Malta, two miles from Leadville, by A. R. Meyer, but was not successful. It was succeeded by the Harrison Reduction Works, in 1878. The La Plata began with one furnace in June, 1878, and in 1879 had four furnaces in active operation. These furnaces used charcoal for fuel, and, because of hot tops, suffered a tremendous loss in lead and silver. This difficulty was overcome by the erection of 50 single-bank 10-ft. beehive ovens at Crested Butte, Colo., in 1880. The slack coal sent to these ovens was very pure, and yielded a coke carrying as little as 4.5 per cent. ash. Among the pioneers in the Leadville district were Grant, Eddy, James, Billings, Eiler, and Dickson. To these men the West owes the present expansion of its mining industry, and the erection of metallurgical processes for the treatment of precious metals. On Mar. 1, 1876, Pueblo was connected to the Atchison, Topeka & Sank Fe by the Pueblo & Arkansas Valley branch. The first smelter was erected in Pueblo by Mather and Geist. This modest plant grew into the immense Pueblo Smelting and Refining Co., now a part of the American Smelting and Refining Co. Coke for these small furnaces was made from unwashed Engleville coal, in 186 single-bank 12-ft. ovens at El Moro, in the Trinidad district, and it was not uncommon for the percentage of ash to exceed the percentage of fixed carbon in the coke. On Jan. 23, 1880, the Colorado Improvement Co. consolidated

Jan 1, 1920

By D. M. Boulin, E. S. Greiner

Single crystals of vanadium were bent at 293" and 77°K to a maximum fiber strain of about 1 pct. Analysis of slip line and etch markings of- crystals deformed at either temperature show the slip planes are {112}. The slip directions at 298° and 77°K, deterwined from the asterism axes of rotation of crystals compressed in a {110} direclion, were (111). Etch pits, associated with dislocations, were observed in the plastically deformed vanadium. There was no evidence of mechanical twinning. THIS paper presents results on single crystals of vanadium plastically deformed by bending and compressing at 298° and 77°K. Bcc metals have been observed to slip on {110}, (1121, and (123) planes while the slip direction has invariably been found to be ( 111) 1 Lindley and smallman2 have studied the deformation intension of polycrystalline vanadium between 298° and 20°K and reported that at and above 77°K the deformation is predominantly by slip, but at 20°K the deformation is associated with twinning. Later, Edington and smallman3 found that single crystals of vanadium compressed in a (111) direction at 77°K deformed by twinning on { 112}( 111) systems. Clough and pavlovic4 have reported that mechanical twins were observed in vanadium loaded by impact at 77°, 173°, and 195°K, respectively. PREPARATION OF SINGLE CRYSTALS The vanadium single crystals were made from commercial vanadium reported to contain 0.03 pct C, 0.03 pct 0, 0.02 pct N, 0.0X* pct Ca, 0.0X pct Si, proximately 0.8 cm diam, 4 cm long and were grown in (100) and (110) directions. A crystal for studies of etch pits was gound to have a face parallel to a {l00} plane by the Bond crystal-orienting technique.7 In order to avoid straining, the crystals were placed on the steel mount with a low-melting organic compound (glycol phthalate) before grinding. Crystals for the bending experiments were ground to have the four side faces parallel to ( 100) planes. The crystals were electropolished8 in 10 pct H2So4 using a current density of about 3 amp per sq cm to remove the strained surface material. The crystals were bent slowly by three-point loading in a stainless-steel jig designed by Sylwestrowicz.9 The end rollers of the jig were 3.8 cm apart. DEFORMATION AT 298°K The bent vanadium crystal, after removal from the jig, had a radius of curvature of 20.4 cm over the 2-cm length close to the center loading roller, where the maximum bending moment occurred. This radius of curvature corresponded to a maximum fiber strain of 0.9 pet. The side faces contained slip bands as shown in Fig. 1. These bands are straight where the strain is high, top and bottom of micrograph, but are curved on either side of the neutral axis in the center. This curvature of the slip bands in the low-stress area may be due to cross slip. The plastically deformed crystal was subsequently electropolished and then electroetched in 10 pct H2SO4 solution, using a current density of 0.25 amp per sq cm. The structure is shown in Fig. 2. The directions of the traces on two adjoining faces were plotted stereo graphically, Fig. 3.* Since there were two sets of

Jan 1, 1968

By Richard H. Jahns

GRANITIC pegmatite deposits are the chief source of commercial feldspar, sheet mica, beryllium, tantalum-columbium, and lithium minerals, and certain types of kaolin. They also have yielded significant quantities of cassiterite, gems, scrap mica, molybdenite, tungsten minerals, uranium-thorium and rare-earth minerals, and zircon, either directly or as the sources of placer deposits. The output from pegmatite mines in the United States is small as compared to other mineral products in terms of bulk or value, and much of it comprises minor metals and nonmetals. Nevertheless, pegmatite minerals play a vital part in domestic industrial economy, particularly in the ceramic and electrical industries. Numerous special purpose uses also are important, even though they require small quantities of raw materials. Never was United States dependence upon pegmatite mining more clearly emphasized than during World War 11, when greatly expanded demands and uncertainties of foreign sources of supply caused much concern. Such commodities as beryl, tantalite, and sheet muscovite remained high on the critical list for months at a time, and for some minerals there was a real struggle to achieve and maintain a favorable ratio of supply to demand. Satisfactory stock piles of certain sizes and qualities of sheet mica, for example, were not built up until late in 1944, when wartime requirements already had begun to level off or even to decrease. Production of all the strategic pegmatite minerals from domestic deposits during World War I1 constituted only 10 pct or less of the total domestic consumption of these minerals, but the importance of this contribution should not be minimized. Domestic production often represented the difference between increase and further reduction of existing stocks of commodities already in seriously short supply, and in the early stages of the war it was the only assured source if imports were cut off. During the recent war period, the U. S. Geological Survey carried on a program of pegmatite studies in the New England and Southeastern States, in the Black Hills area of South Dakota, in the Rocky Mountain region of Wyoming, Colorado, and New Mexico, and in various parts of Washington, Idaho, Utah, Nevada, Arizona, and California as shown in Fig. 1. Several papers and reports already have appeared as an outgrowth of this work,&apos;-= and others are in preparation. This paper outlines some results of data obtained by the writer during the period 1942 to 1946, when he was engaged in studies of pegmatites in the Southeastern, Southwestern, and Rocky Mountain States. Beryllium Minerals Beryl is the present commercial source of beryllium metal and beryllium compounds, which are used in ceramics, in the preparation of X-ray tubes and fluorescent lamps and screens, in special processes of paint and textile manufacture, and in the optical systems of some electrical instruments. The metal also is used in nuclear physics, chiefly as a source of neutrons. Beryllium is alloyed with aluminum for certain light-metal uses and is a constituent of some nickel and iron alloys. Currently the chief demand, however, is for copper-base alloys, which are exceptionally resistant to fatigue and wear, are responsive to hardening treatments after

Jan 1, 1952