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By Y. Ueda, F. Noguchi, T. Yanagase

The rate of CaO dissolution into slag melts is of great importance in the field of pyrometallurgy. In this study the mechanism of CaO dissolution has been investigated by observing the melt heated on Pt-filament directly through microscope together with a help of X-ray micro analyser to find out a distribution of each element around CaO crystal. The direct observation reveals that the CaO dissolution tends to proceed by the action of molten slag entering between CaO crystal and newly formed 2Ca0. Si02 layer through cracks. The effect of slag composition on the formation of 2CaO- SiO2 layer will be shown as well as the effect of halogenides addition on the destruction of this compound layer.

Jan 1, 1976

By J. D. Hanawalt

Significant strides were made in the year 1948 leading to further recognition of the place of magnesium as a common commercial metal, rather than as just a premium aircraft material. One of the factors contributing to this recognition was the price stability and, in many cases, price reduction of magnesium products in 1948. In contrast to most other metals, manufacturing advances in magnesium outweighed the effects of increased labor and other costs. At the present time, many magnesium extrusions, die castings, and permanent mold castings can be purchased as cheaply as their aluminum counterparts in these forums, though competitive prices for sheet still await the inauguration of a modern tandem rolling mill for magnesium, such as has already been demonstrated.

Jan 1, 1949

By Oliver S. North

Reserves of perlite rock in the western section of the United States are immense. A geological report prepared for the Union Pacific RR showed proved tonnage of over 400 million tons in southern Nevada alone. Yet the perlite industry is not large, and most of the mines are relatively small. There are indications that perlite processing, thus far largely in the hands of relatively small com¬panies, is becoming concentrated in a few large companies. For economic reasons the bulk of perlite sold in crude form has come from three or four pro¬ducers, although many individual operators have sold small quantities to limited lists of purchasers. Perlite is one of ultra-lightweight aggregates. Owing to its outstanding qualities as an aggregate, variety of uses, and ultimate economy of use, it has enjoyed considerable popularity in this country in recent years. Marked foreign interest also has been evinced in this material.

Jan 2, 1955

By E. N. Cameron, H. M. Bannerman

During the years 1942-1934, about 125 New England deposits were mined for sheet and punch mica, and many others were briefly prospected. During this period the Geological Survey, United States Department of the Interior, carried on detailcd studies of the deposits and the pegmatite bodies that contain them. The primary purpose of the studies was to provide geological information that would contribute toward efficient mine development and operation. The studies were aimed directly at practical production problems. Detailed maps showing the structure of the deposits were prepared, and geological findings were closely correlated with data on specific yields and costs of mining and processing. The result is information that permits a reasonably accurate appraisal of the mica deposits of New England and the mining industry that they support. At a time when the future of the industry is in doubt, it seems desirable to submit this appraisal for consideration. Domestic mica deposits supply only a small fraction of the country's needs in normal times? for only the richest domestic deposits can compete with the low-cost mines of India and Brazil. However, the possibility that this country may be cut off from its supplies in time of war gives domestic deposits an importance much greater than their peacetime production would imply. New England supplied about 22 per cent of domestic output in 1943 and 1944, the peak years of wartime production. Its actual contribution to the war effort was greater, for the proportion of sheet mica of high quality in the New England product is higher than the average for domestic mica. The data analyzed below were collected for the Geological Survey by D. M. Larra-bee, A. H. McNair, J. J. Page, V. E. Shai-nin, G. W. Stewart, and the co-authors of this paper. The cooperation of officials of Colonial Mica Corporation and of mine operators and owners in furnishing information is gratefully acknowledged. D. M. Larrabee, A. H. McNair, and V. E. Shainin have made various suggestions based on critical reading of the manuscript. Analysis oF Warrtime Operations In considering the data presented in this report, it must be remembered that the scale of mica operations is very small compared with that of many other mining industries. The typical New England mica mine of 1943 and 1944 was worked by a crew of five or six men. Equipment was varied but on the whole extremely simple. The first stage of operation at a deposit was normally opencut mining. Drilling was done mostly with jackhammers powered by portable compressors driven by gasoline engines. Muck was shoveled by hand into buckets with a capacity of 45 to 35 ton and commonly hoisted by derrick to a dump adjacent to the cut. As operations were carried to greater depth, and the tram sition to underground mining was made, these methods were modified to a degree depending largely on the attitude of the deposit mined. At steeply dipping deposits,

Jan 1, 1948

By H. M. Bannerman, E. N. Cameron

During the years 1942-1934, about 125 New England deposits were mined for sheet and punch mica, and many others were briefly prospected. During this period the Geological Survey, United States Department of the Interior, carried on detailcd studies of the deposits and the pegmatite bodies that contain them. The primary purpose of the studies was to provide geological information that would contribute toward efficient mine development and operation. The studies were aimed directly at practical production problems. Detailed maps showing the structure of the deposits were prepared, and geological findings were closely correlated with data on specific yields and costs of mining and processing. The result is information that permits a reasonably accurate appraisal of the mica deposits of New England and the mining industry that they support. At a time when the future of the industry is in doubt, it seems desirable to submit this appraisal for consideration. Domestic mica deposits supply only a small fraction of the country's needs in normal times? for only the richest domestic deposits can compete with the low-cost mines of India and Brazil. However, the possibility that this country may be cut off from its supplies in time of war gives domestic deposits an importance much greater than their peacetime production would imply. New England supplied about 22 per cent of domestic output in 1943 and 1944, the peak years of wartime production. Its actual contribution to the war effort was greater, for the proportion of sheet mica of high quality in the New England product is higher than the average for domestic mica. The data analyzed below were collected for the Geological Survey by D. M. Larra-bee, A. H. McNair, J. J. Page, V. E. Shai-nin, G. W. Stewart, and the co-authors of this paper. The cooperation of officials of Colonial Mica Corporation and of mine operators and owners in furnishing information is gratefully acknowledged. D. M. Larrabee, A. H. McNair, and V. E. Shainin have made various suggestions based on critical reading of the manuscript. Analysis oF Warrtime Operations In considering the data presented in this report, it must be remembered that the scale of mica operations is very small compared with that of many other mining industries. The typical New England mica mine of 1943 and 1944 was worked by a crew of five or six men. Equipment was varied but on the whole extremely simple. The first stage of operation at a deposit was normally opencut mining. Drilling was done mostly with jackhammers powered by portable compressors driven by gasoline engines. Muck was shoveled by hand into buckets with a capacity of 45 to 35 ton and commonly hoisted by derrick to a dump adjacent to the cut. As operations were carried to greater depth, and the tram sition to underground mining was made, these methods were modified to a degree depending largely on the attitude of the deposit mined. At steeply dipping deposits,

Jan 1, 1948

By Fred C. Bond

The process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. Formula for Ball Wear Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1943

By Fred C. Bond

The process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. Formula for Ball Wear Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1943

By Ernest F. Burchard

PAGE. I. Introduction,........... 75 II. Outline of the Geology......... 76 1. Stratigraphy............ 76 A. Clinton Formation........ 77 2. Structure...........82 3. The Ore..........85 A. Character............ 85 B. Geographic Distribution....88 III. Local Descriptions........... 88 1. Birmingham District.......... 88 A. Topography and Its Relation to Industrial Development... 88 H. Distribution and Structure of Formations.... 89 C. Divisions of the Birmingham District. 95 Division A (Description of the Ore-Beds), . 95 Division B.........105 Division C.......... 106 Division D,..107 Division E,...........108 Division F........ 111 Division C.......... 112 D. Mining .Development.... 113 2. Northeast Alabama........114 IV. Possible Origin oF the Ore......... 119 V. Relation of Origin to Quality and Extent of Ore... 122 VI. Estimates of Ore-Reserves,......... 125 1. Method of Making Estimates......... 125 2. Data and Results....126 VII. Production and Consumption oF IRon-ORe,.... 132 I. Introduction. Brief and interrupted studies of the Alabama Clinton iron-ores have been made within the last four years by members of the IT. S. Geological Survey. Reports on the progress of this

Jan 1, 1910

By Holt, Grover J.

PRIOR to :1937 any discussion of mining and transportation in the iron mines of Minnesota would have been limited largely to conventional methods which have been used for years in the iron ore industry. Today, however, an inspection trip to the crest of almost any open pit on the ranges will re- veal great progress underground mining and the transportation of underground ore have also developed rapidly and if and when underground mining of iron ore again becomes generally economically feasible; these mining methods will probably witness a transformation equal to that which has taken place in the open pits.

Jan 1, 1941

BECAUSE of the impetus given to placer mining since the price of gold was advanced to $35, several types of small dredges have made their appearance, especially in the Lincoln and Oroville areas of California. Some of these are known as "doodle bugs," and have been given considerable publicity, though many believe their performance has been overrated and that complete costs of construction and operation, if known would not put them in so favorable a light. Fig. 1 is a doodle bug owned by E. M. Clark and operated near Lincoln, Calif. It is understood that it was abandoned because of inability to handle deep ground. A similar machine that has been operated-profitably by Comstock Placers is shown in Fig. 2.

Jan 1, 1938

J. E. Johnson, Jr., Glen Wilton, Va. (communication to the Secretary*):—Mr. Meissner announces early in his paper that one of its purposes is the discussion of my paper entitled, Notes on the Physical Action of the Blast-Furnace,' with which he disagrees in part; and as the second stage of the discussion of this important subject has centered around his paper, some reply by me may not be amiss. Unfortunately, Mr. Meissner has not indicated a single statement or conclusion in my paper that he wishes to controvert; but as there is evidently a difference of opinion between us I will disregard this fact, and will discuss those conclusions of his that seem to me not to be justified by the facts of general practice, or even by the data which he produces to support them. Let me say, however, that I am a believer in the dry-air

Jan 1, 1908

By R. S. Dean

REQUIREMENTS for war materials have led to large scale experimentation upon metallurgical innovations. It is of interest to inquire what this may contribute of permanent value to our existing technology, as innovations adopted during war are apt to be discarded promptly at its end. This is because utilization of substandard ores usually requires a new technology for ore treatment, and a new use-pattern for employment of the products. Thus two very different problems are involved: first, devising a process; then, adopting its products by industry, with readjustments of the use-pattern if necessary. A new process may be as good or better than an old one, but the readjustments required for use of its products may prevent its general adoption if this implies scrapping existing plants and investing much additional capital. Metallurgical innovations are of three kinds: I. The use of substandard material in processes already established; 2. The grading-up of substandard material to render it more suitable for established processes; 3. The adjustment of technology and use-pattern to the raw materials that we have.

Jan 1, 1945

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By James Aston

A PROPER consideration of this subject is not confined to the technical channels of production and metallurgy. It concerns an industry, and should cover economic aspects which are of material importance in any program of development. The discussion may logically be treated under three subdivisions, as follows: (1) manufacture, (2) characteristics related to quality of material; (3) adaptability and exploitation of product. MANUFACTURE OF WROUGHT IRON The manufacture of wrought iron is the most ancient art of the ferrous metal industry. The eighty years or less of existence of processes identified with our modern "Age of Steel" is a relatively brief interval compared with the several thousand years associated with the production of wrought iron by man. From the primitive early methods of production, manufacture for many centuries followed the line of direct reduction. There were developments as experience was gained through the years; but man's needs for a strong, ductile, forgeable product were met by reducing the ore to metallic iron in a single-stage operation. Following the development several centuries ago of what has become our modern blast-furnace operation, manufacture of wrought iron was gradually transformed into a two-stage method of first producing cast iron and then refining this to the desired degree of forgeability; the forerunner in principle of today's scheme of manufacture of steel. The product retained the essential characteristics of highly refined base metal with iron-silicate slag incorporation, which were associated with the material resulting from direct reduction methods. Cort's invention of the puddling process in 1784 is a landmark in wrought-iron manufacture. It consisted essentially in adapting a coal-fired reverberatory furnace to the refining operation; thus lifting the industry out of the slough of

Jan 1, 1935

By Leonid V. Azároff, H. N. Murty

In the course of investigating the soft X-ray absorption spectra of Ni-A1 alloys, Das and ~zfiroff' observed an anomalous brittleness in solid solutions containing 3 to 5 at. pct Al. The brittle alloys also had anomalously larger lattice constants' and the fine structure at the nickel K edge of an alloy containing 3.96 at. pct A1 unexpectedly resembled that of NiA1 more closely than that of a solid solution containing 5.51 at. pct Al. This led them to suggest the possibility that short-range ordering was produced during the homogenization anneal to which each specimen was subjected, similar to that observed in dilute solutions of vanadium and of chromium in nickel: as the principal cause of embrittlement. It was decided to repeat the above measurements on several alloys in this composition range in order to test the above hypothesis and to establish the effect of heat treatment on the alloys' properties. Three solid solutions in this range were prepared containing, respectively, 3.16, 4.00, and 4.54 at. pct Al, in addition to alloys containing 6 and 9 pct. All samples were annealed in vacuum at 1800°F for 100 hr and then furnace-cooled to room temperature, as in the original study. The lattice constants of these alloys are shown by open circles in Fig. 1 and can be seen to fit quite closely the curve established by the previously measured values, indicated by solid circles. (The experimental errors are of the order of the size of the circles, +o.oo~R.) The three alloys containing 3 to 5 at. pct A1 were found to be quite brittle, as previously reported. In order to test the possibility of ordering, these three solid solutions were again heated to 1800°F and, following a few hours at that temperature, were quenched directly to room temperature. All three alloys lost their brittleness. In order to verify the proposed ordering hypothesis, it was decided to subject each sample to several cycles of quenching and annealing (disordering and ordering). After some experimentation, it was established that reproducible results could be obtained by anneal-

Jan 1, 1968

By Fred C. Bond

THE process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in, common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. FORMULA FOR BALL WEAR Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1940

By W. F. Hosford

A series of aluminum single crystals was subjected to axially symmetric flow by drawing through dies. The orientation dependence of the drawing stress, which indicates the resistance to this type of flow, compares reasonably with predictions of Taylor and of Bishop and Hill. Measured lattice rotations likewise are generally consistent with theory. The most successful analyses of the plastic behavior of polycrystalline metal and its relationship to single crystal behavior are those of Taylor1-3 and of Bishop and Hill.4-6 The purpose of this paper is to provide a critical test of some of the basic assumptions involved in these theories. Both treatments apply to fcc metals and assume the shape change of each grain in a polycrystal to be the same as that of the polycrystal as a whole. Thus for a randomly oriented polycrystal extended under uni-axial tension each grain is assumed to undergo axially symmetric flow. dey = dez = -1/2dex, deyZ = dezx = dexy = 0 [l] where x, y, and z are a set of orthogonal axes, x being the tensile axis. Although [011.] oriented grains in bcc and fcc metals may depart markedly from this ideal behavior,7,8 the assumption is probably quite reasonable for most grains. Under a uniaxial tensile stress, ox, the work dW per unit volume expended in producing an increment of axial strain dex is, dW=oxdex [21 Since this work is expended in slip, dw =STi dyi 131 where Ti and yi are the shear stress and shear strain on the active slip systems. In both analyses Ti is taken to be the same on all slip systems, and dependent only on the total prior shear strain on all systems, so dw = Tdy [41 where t is the shear stress required for slip and y is the sum of the shear strain yi on all slip systems. Combining 121 and [4] and defining M = oX/T The ratio M is a generalized Schmid factor. It relates the tensile stress required for axially symmetric flow, ox, to the basic shear stress, 7, and it also expresses the ratio of crystallographic strain, y, to the tensile strain, Ex It depends only on the orientation of the crystal. Taylor evaluated M for various orientations by finding the least value of dy/dEx which could satisfy the shape change. Bishop and Hill, on the other hand, found M by considering the relative work (1/T)dW/dEx expended by stress states which could activate enough slip systems to produce the shape changes. The results of both methods appear to be equivalent, although certain omissions were made in Taylor's original work. The orientation dependence of M, calculated by the second method,9 is shown in Fig. 1. Taylor used the average 2= 3.06 for all possible orientations to predict the tensile stress-strain curve (oxvs Ex) for a random polycrystal from the shear stress-strain curve (t vs y) of a single crystal. Changes in M from lattice rotation were neglected so points on the ox vs ex curve were simply taken at ox = 3.06t and e = y/3.06 from corresponding points on the t vs y curve. Recent extension of the analyses of Taylor and of Bishop and Hill to crystallographically textured metals has been used to relate plastic anisotropy to textures, and to predict the potential texture hardening that could result from texture control.9 Unfortunately there have been relatively few experimental tests of the underlying theory. Taylor found that the tensile stress-strain curve of polycrystalline aluminum did agree reasonably well with that predicted from a single-crystal T-y curve. Had the single crystal undergone easy glide, how-

Jan 1, 1965

By J. B. Mackintosh

In a recent paper read before the Institute on this subject, Mr. G. C. Stone advances the theory that the precipitate obtained in Williams's volumetric process,* by treating the boiling nitric acid solution of a manganese salt with potassic chlorate., is not pure MnO2, but approximates more closely to the composition 10Mn02+Mn0. As the value of the process and the accuracy of our results mould depend on whether this was the fact or not, it has seemed to me, and to my associates, Messrs. Beebe and Colly, that it would be of importance to ascertain the composition of this precipitate, and to that end the following series of experiments has been undertaken. These experiments have all been based on the considerations: 1. That potassic permanganate has an oxidizing power equivalent to five atoms of oxygen for every two of manganese : K2Mn2O8 = K2O.2MnO.O5. 2. That the same amount of manganese in the state of binoxide has an oxidizing power equivalent to two atoms of oxygen : 2MnO2 = 2MnO.O2. If, then, we take a solution of permanganate of unknown strength, and reduce it to binoxide, the oxidizing power of the binoxide formed will be equal to that of two-fifths the quantity of the permanganate solution originally taken. While, if the precipitate obtained should not be binoxide, but an indefinite or definite mixture of bin- and mon- oxides, then, from its equivalent oxidizing power, we can calculate its composition. The analyses were conducted in the following manner. The amount of permanganate taken was decomposed with hydrochloric acid, and concentrated to expel the excess of water. Sufficient excess of nitric acid was now added, and the solution was boiled until all the hydrochloric acid was destroyed. The manganese was then precipitated by potassic chlorate; and, after standing some time to cool—a pre-

Jan 1, 1884

By Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen' has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.'2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"'12 were made to join the inner and outer titanium

Jan 1, 1968