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By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954

By Robert Roberts

(Butte Meeting, August, 1913.) IN order to obtain data on the thermal effect of the blast-furnace jacket and oil the water consumption in these jackets a series of tests were run on the 56 by 180 in. blast furnaces at the Great Falls Reduction Department of the Anaconda Copper Mining Co., at Great Falls, Mont. The arrangement of the jacket is shown in the transverse section of one of the furnaces (Fig. 1) on which the tests were made. The nose, spout, and breast jackets have independent water supplies and discharges. The end and side jackets are connected in pairs, as regards water supply, the feed water entering at the bottom of the lower jacket and overflowing into the bottom of the jacket immediately above it, and discharging into an independent overflow pipe for each pair of jackets. Tests were run on the main side and end jackets, the breast jacket, the spout, and the nose. Measurements were taken of the quantity of water discharged per minute and the rise in temperature of the water in its passage through the jacket. The product of these two results, expressed in the proper units, evidently gives the number of units of heat removed per minute by the water. Sufficient work was done on each type of jacket to determine its behavior under different conditions, and the results from each set of conditions were checked by repeating the work from three to six times.

Jan 7, 1913

By O. T. Marzke, Robert F. Mehl

A study of the structures arising from the decomposition of the ß solid solutions in the Cu-Zn and the Cu-A1 systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution— the Widmanstätten structure—-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the ? phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series—that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-—which at present seems the only a1ternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the ß and in the precipit'at.ion of the y phase from the y in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point, of view.

Jan 1, 1931

By H. P. Leighly, J. W. Marx, H. L. Walker

A relationship between recrystallized grain size and prior deformation is predicted from elementary statistical considerations, and reasonable agreement with experiment is obtained. RECRYSTALLIZATION phenomena have received much theoretical and experimental attention, and very adequate discussions of the various mechanisms suggested have been given by Anderson and Mehl,' Cook and Richards,' and Burgers," and others. It suffices to note here that the initial concepts fitted one of two general hypotheses: I—The new crystals are nucleated within microscopic regions at which there is a concentration of internal stress, i.e., volume elements of maximum strain energy. 2—The new crystals have their inception in volume elements of minimum strain energy. In a comprehensive early review of the subject, van Arkel' considered both possibilities and came to the conclusion that hypothesis 2 was inconsistent with the experimental fact that the number of nu-cleations increased with increasing deformation. He suggested that, if allowance was made for a preliminary atomic rearrangement at the points of large internal strain, hypothesfs 1 provided the more reasonable concept. Following the initial observations of Collins and Mathewsonb nd Crussard,Y he systematic X-ray investigations of Cahn' and Guinier and Tennevin" established the existence of a polygonized structure in metals that had been cold-worked, and subsequently annealed, under conditions such that re-crystallization did not occur. This new experimental evidence by no means disproved the first nucleation hypothesis, a fact recognized by both Beck" and Cahn,10 who independently suggested nucleation mechanisms based on the idea that regions of large strain might polygonize before the bulk of the less deformed material. These mechanisms, together with others recently proposed," are dependent upon the prior existence of some degree of polygonization in the deformed material. On the other hand, a critical examination of the published data leads to the supposition that polygonization may not be the necessary precursor of recrystallization, but merely its favored energetic competitor. In regions where the lattice distortion is not too severe, the limited adjustment afforded by polygonization may permit the lattice to drop to a relatively stable low energy state in which the nucleation of a new crystal becomes improbable, even at elevated temperatures. Such structures, of course, might provide a fertile field for the growth of nuclei, if these could be introduced. In regions of concentrated lattice distortion, polygonization alone may not be able to accomplish an adequate strain reduction, and in these volume elements sufficient thermal activity permits the more drastic atomic rearrangement involved in nucleation. Completely polygonized structures are known to withstand extended heating close to their melting points," with no other effect than a slow enlargement of some of the subgrains at the expense of others. Once started, macroscopic recrystallization might be expected to go to completion in a matter of minutes under similar heat treatment. Crussard12 and his coworkers have found that recrystallization may occur in single crystals of impure (about 99.7 pct) aluminum without any detectable prior polygonization. The indication here is that large Cottrell impurity atmospheres inhibit dislocation movement, thus suppressing polygonization to such an extent that the alternative process, recrystallization, dominates the lattice restoration. Experimental studies relating recrystallization directly to stored energy have not, at the present time,

Jan 1, 1954

By T. M. Dr. Drown

(Read at the Philadelphia Meeting, February, 1878.) ZINC is, as is well known, very brittle at a temperature of about 210° C. (410° F.), and may then be readily pulverized in a mortar. By sifting it may be obtained of uniform grain. I have been accustomed to prepare products passing through 40, 60, and 80-mesh sieves, and also by bolting through a fine handkerchief. The principal analytical uses to which I have hitherto applied this material are to the reduction of iron directly from the ore by heating it with the pulverized zinc, and the reduction of ferric to ferrous compounds in solution. In the first case the pulverized ore, 0.5 gram or less, is intimately mixed with about ten times its weight of the pulverized zinc (the finer the zinc the better), in a porcelain crucible, and this mixture is covered with about the same amount of zinc. The crucible is then heated at the top of the flame of a Bunsen burner, at a dull red heat, for about ten minutes. The crucible should not be covered. When cool, the crucible, with its contents, is placed in a flask treated with hot dilute sulphuric acid, and brought quickly to a boil. The zinc and reduced iron are dissolved in a few minutes and the flask is then tightly corked and allowed to cool. When cool, the iron is directly titrated by potassium permanganate.

Jan 1, 1878

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By T&apos Ke, ing-sui

NUMEROUS investigators have observed that internal friction accompanies cold-working of metals and the effect of annealing is to reduce this internal friction.1,2 However, - most of the experiments were made at high stress amplitudes and the principal purpose was to study the increase of internal friction as a result of the applied cyclic stress during measurement. In order to study the internal friction introduced by cold-working applied prior to the measurement, the stress level applied during the measurement of internal friction must be sufficiently small. The results of measurement are significant and can be used for a base of comparison only when the applied cyclic stress is so small that the internal friction is independent of stress amplitude. Internal friction of cold-worked metals under small stress level has been studied by a number of workers8 -" he internal friction was measured around room temperature with a frequency of vibration of the order of kilocycles per second. The purpose of this paper is to report a study of the change of internal friction when severely cold-worked aluminum was annealed at successively higher temperatures until it was completely recrys-tallized. The measurements of internal friction were made over a range of temperature extending from room temperature up to the temperature of prior anneal. The frequency of vibrations used was about one cycle per second. The apparatus used for the internal friction measurements to be reported in this paper was a torsion pendulum with the specimen in wire form as the suspension fiber. The description of this apparatus and the method of measurement have been previously given.7,8 The applied stress was sufficiently small SO that the magnitude of internal friction is independent of stress level at each temperature range concerned. Corresponding to this stress the maximum shearing strain on the surface of the specimen is of the order of l0-5 and lower. The in- ternal friction (Q-1) is reported as 1/p times the logarithmic decrement. Internal Friction Versus Temperature of Anneal: Fig. 1 shows the internal friction measurements performed upon 99.991 pct aluminum subjected to 95 pct reduction in area. The final diameter of the wire is 0.033 in. This figure gives a general survey of the effect of temperature of anneal and of temperature of measurement. The internal friction of the cold-worked specimen was first measured at room temperature. It was then annealed at 50°C for one hour and the internal friction measured at 50°C and at room temperature. The same wire was successively annealed at higher temperatures for one hour and measurements were taken at the annealing temperatures and lower temperatures as before. Such a procedure was followed in order to stabilize the internal friction at the temperature of measurement so that during the measurement which generally takes about half a minute, there is no detectable change in internal friction. This series of measurements .was made up to 450°C. After each annealing a short test piece of the specimen, which had received the same past thermal and mechanical treatments, was taken out for metallographic examination. It is seen from fig. 1 that up to the annealing temperature of 250°C we have the following observations: for any given temperature of measurement, the internal friction is lower the higher the temperature of prior anneal. When the annealing temperature is 290°C or higher, the internal friction at the annealing temperature drops abruptly to a value which is much smaller than that for the previous curve. Metallographic examinations showed that the recrystallization of the specimen was completed after the annealing at 290°C. Fig. 1 shows that, as far as internal friction is concerned, there is no abrupt transition between the processes of recovery and recrystallization. Averbach has also reached the conclusion that recovery may be a process analogous to recrystallization on the basis of X ray extinction measurements in brass." The effect of annealing temperature upon the internal friction at room temperature is shown by curve I of fig. 2. In this figure the internal friction at room temperature was plotted as a function of annealing temperature. It is seen that the internal friction decreases rapidly at first with an increase

Jan 1, 1951

By AIME AIME

THE section delegates assembled Monday morning with the incoming president, W. H. Bassett, in the chair and F. W. Bradley as vice-chairman. The secretary called the roll and urged the delegates to become familiar with the activities of the Institute. He explained the allotment of funds to local sections and the uses to which these funds may be put. He also announced plans for travel by Mr. Bassett and asked the delegates to confer with him as to meetings en route. An invitation was extended for all section delegates to attend the Directors' dinner Wednesday evening. He suggested that local sections hold a meeting once a year under the auspices of each division of the Institute. He further explained the system of choice of publications by members. The question of licensing of engineers was brought up, and the consensus of opinion among the membership was asked for. Because the matter is controversial, no official action has been taken and it was suggested that the' local and State sections act separately in this regard. A. B. Parsons, the assistant secretary, next spoke. In his remarks he indicated surprise that many prominent mining men still did not belong to the Institute, and urged that section delegates make up a list of such prospective members and send it in to the office for study by the New York staff. He also asked that re- ports of all meetings be turned in for publication in MINING AND METALLURGY, and said that the reports

Jan 1, 1930

By Zay Jeffries

Page Introduction............................. 474 Nature of Experiments ........................ 476 Materials Used in Experiments..................... 476 Description of Samples........................ 476 Details of Tests and Apparatus .................... 486 Determination of Elongation...................... 488 Determination of Reduction of Area .................. 488 Results of Tests........................... 489 Quantity and Arrangement of Amorphous Phase............. 497 Properties of Amorphous and Crystalline Phases............. 501 Intercrystalline Fracture........................ 530 Trans-crystalline Fracture....................... 531 Rupture ............................... 535 Explanation of Beilby's Results..................... 536 Mechanical Properties of Copper Wires................. 537 Mechanical Properties of Tungsten Wires................ 542 Mechanical Properties of Iron Wire................... 546 Effect of Diameter of Wire on Mechanical Properties........... 554 General Considerations on Properties of Metals at Very Low Temperatures .. 556 General Considerations on Physical Properties of Complex Alloys...... 557 Summary.............................. 559 Discussion.............................. 562 Introduction DuRing the period 1914 to 1916. the writer observed many times that tungsten wire could be drawn hot until it became brittle but on cooling to room temperature it became ductile again. In searching the literature for parallel cases. it was found that Beilbyl had produced hard-drawn wires of gold. silver. and copper that showed less than 1 per cent.

Jan 1, 1919

By Leo Behr

RECENT years have seen important practical advances in the construction of recording instruments for use with thermocouples. The difficulties of the problem will be appreciated when it is remembered that a 10° F. change in temperature of a base-metal couple at 1500° means a change in the electromotive force of about 0.00035 volt. In a circuit having a resistance of 350 ohms, this means a change in the current of 0.00000,1 amp.; and despite this requirement of great sensitivity the instruments must be sufficiently robust to withstand the rough usage which is so often their lot. Two methods are in common use for the measurement of the electromotive force produced by a thermocouple: 1. The milliammeter method, in which the current produced by the thermocouple in a circuit of known resistance is measured and from. this the electromotive force is deduced by Ohm's law. 2. The potentiometer method in which a known potential difference is opposed to the thermocouple electromotive force. The use of thermocouple and milliammeter for measuring temperature introduces some possible sources of error, for the reading depends on a number of factors, including the following: (1) Electromotive force set up at the hot junction, (2) electromotive force set up at the cold junction, (3) resistance of the circuit including thermocouple, lead wires, and meter, (4) field strength of magnets, (5) strength of controlling springs in meter, (6) friction at pivots, of pointer on paper, etc. It is obviously necessary to so design and maintain the installation that the reading is independent of all the factors except the first. The electromotive force set up at the cold junction can easily be taken care of provided it is constant. This has been approximately accomplished by burying the cold junction in the ground or actually secured by locating it in a container, the temperature of which is kept constant by means of a thermostat.

Jan 9, 1919

By R. W. Raymond

Through the courtesy of Mr. James H. Mayo, a member of the Institute, who is in charge of the operations of the Mindrinetti Company in the Saramacca district of Dutch Guiana, I have received specimeris of certain peculiar pseudomorphs of limonite after pyrite, which occur abundantly in the auriferous deposits of that. region.* I am indebted to Mr. H. Tweddle, a geiltleman- connected with the same company, for some particulars of interest con-

Jan 1, 1899

By E. P. Fleming

COMPARED to the situation abroad, the domestic industry continues to lag both as regards the production and consumption of newly mined lead. During 1938 we produced and consumed slightly over 20 per cent of the world output, whereas ten years ago the figure was nearly double this pro- portion. Labor difficulties and absence of demand were chiefly responsible for the general inactivity. In the foreign field, in spite of low metal prices, production and consumption of lead equaled or exceeded all previous records. Practically all the large companies, with the exception of those in Spain, increased operations, though it should be noted that the foreign lead mines have higher-grade ores than domestic mines. In view of the rapid expansion of the foreign industry, it is natural to expect greater progress abroad, particularly in process metallurgy.

Jan 1, 1939

As already announced, the Arizona Meeting of the Institute is to be held from the 18th to the 25th of September. There will be a special train from New York City to Arizona and return, to take members and guests of the Institute to the meeting. The Committee in charge consists of Walter Douglas, Chairman, Cleveland E. Dodge, John C. Greenway, Arthur S. Dwight and Julius Kruttschnitt, Jr., and while the plans of this Committee are not complete, it may be announced that the train will be run with the requisite number of Pullman, dining and baggage cars to accommodate those who desire to go, which will accompany the party during the entire week of the Arizona Meeting as per the following program, including, of course, the visit to the Grand Canyon. As soon as details have been worked out, a circular will be issued giv¬ing full information concerning the trip.

Jan 7, 1916

By AIME AIME

AT the meeting of the Iron and Steel Division at Cleveland, Sept. 10-12, the morning of Thursday, Sept. 12, has been set aside for an excursion to visit the ore docks, blast furnaces, and steel plants. A special train, made available through the courtesy of Appleton Cleveland, general superintendent of the Pennsylvania Railroad, will leave the siding near the Auditorium at 8.35 a. m. The trip will be free, but tickets must be' obtained in advance at the booths for registration for excursions at the Auditorium. An hour will be spent at the docks, an hour at the Central blast furnaces, and two hours at the Cuyahoga works of the American Steel and Wire Co. A buffet luncheon will be served, with the compliments of the Pennsylvania Railroad Co., on board the train en route. At the Tuesday morning session, Sept. 10, a motion picture showing the operations in making wrought iron by the Aston process will be shown for the first time.

Jan 1, 1929

By Albert L. Toenges

COAL mining technique progressed slowly until the advent of mechanized mining. The cutting machine was a forward step, but had only a limited effect upon improving the percentage of coal recovery. Previously, the physical fitness of the loaders and the total output of the miners fixed mine production. The miner was an independent contractor and supervision over his working place was superficial. Rising costs and the inroads of substitute fuels demanded increased output per man to lower the unit production cost. Therefore, the amount of coal loaded mechanically in underground bituminous mines has risen from 0.3 per-cent in 1923 to 7.4 in 1929, to 20.2 in 1937, and to 48.9 percent in 1943. When loading devices were introduced it became necessary to adapt them to existing systems of mining, or to alter the mining system to fit the machine. An increased amount of supervision was required as output depended upon proper operation of the machine rather than on the physical fitness of the individual.

Jan 1, 1946

By William Fink

Two of the aluminum-alloy systems previously studied-the alumi-num-titanium and the aluminum-chromium-exhibit a peritectic reaction at the extreme aluminum end of the diagram. Preliminary work indi-cated that the aluminum-zirconium and certain other aluminum systems were similar in this respect. The present paper, the twentieth of a series from the Aluminum Research Laboratories, reports the results of a recent investigation of equilibrium relations in aluminum-zirconium alloys of high purity, which confirm the preliminary observations. PREVIOUS INVESTIGATIONS There has been only one investigation of the aluminum end of the aluminum-zirconium system. Sykes1 prepared and studied alloys containing 0 to 70 per cent Zr. The lowering of the freezing point of aluminum by the addition of zirconium was found to be very little, if any (less than 2°C.). He placed the solid solubility of zirconium in aluminum at room temperature between 0.57 and 0.97 per cent. A few other investigators have attempted to determine the com-position of the intermetallic compounds occurring in this system. Hönigschmid2 obtained the compound ZrAl3 as a by-product during the preparation of ZrSi2. He made no attempt to prepare other aluminum-zir-conium compounds. Weiss and Newmann3 prepared an alloy by heating aluminum with a double fluoride of potassium and zirconium. When this alloy was treated consecutively with caustic soda and hydrochloric acid, there was a residue, which contained approximately 72 per cent Zr and 28 per cent Al (Zr3Al4). Marden and Rich4 prepared an alloy in the same way, treated it with caustic soda, and obtained a residue of silver-white crystals, which contained 70 per cent Zr and 30 per cent Al (Zr3Al4).

Jan 1, 1939

Discussion of the paper of John H. Hall, presented at the New York. Meeting, October, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1247 to 1256. WILLIAM 'R. WEBSTER, Philadelphia, Pa.:-I would like to call ,attention to the fact that the results of the ordinary tension and bend tests do not always give us the information we want even if we figure out the amount of work done. You want a bending test of sufficient width and full thickness. In the case of eyebars, for instance, I have had experience with a 10- by 1-in. eyebar which gave perfectly good results in a full-size test of the finished bar. The 10- by 1.5-in. and 10- by 1.75-in. eyebars from the same heats-of steel were absolutely worthless in full-size tests. The narrow bending tests from all these bars gave good results. Bat after going into the matter fully, we found that if pieces about 3 in. wide and full thickness were used for the. cold bending tests, the heavier material would not stand this test, but failed. That is, in order to check the quality of the rolled bar you should have a wide piece of full thickness for cold bending, as the narrow pieces give misleading results. J. E. JOHNSON, JR., New York, N. Y. :-I would like to ask if there have been any tests made to compare the results of Charpy tests with the true dynamic test similar .to the Wohler test, except that the piece is subjected to a tensile or compressive stress and to alternating stresses in addition, at the same time. This seems to me to approach more nearly than any other test to the conditions of actual service. where the piece is under a fixed initial stress plus a highly variable and often alternating stress. Some tests were made on this plan in England within a year or two. The test piece was Subjected to either a tensile or compressive stress of known amount and simultaneously to alternating stresses in addition. Such a. test as this gives information which we cannot get by a tensile test or even from the tensile strength multiplied by an. elongation. Such tests, however, are exceedingly tedious and require long periods of time in order to obtain valuable results. If material could be subjected to these dynamic tests and the same material to the. Charpy shock test, and if some reasonable qualitative relation could be established between the results of the two tests, then we could assume that the shock test, which is so simple and easy to make, was a measurably accurate test of the dynamic qualities of the material. At present it does not seem

Jan 12, 1913

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958