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By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By F. W. Jessen, N. Mungan

The plastic flow characteristics of clay water suspensions were first recognized by Binghaml in 1916 and further studied by Ambrose and Loomis' in 1931-1932. Many physical and chemical properties of clay suspensions are deeply influenced by particle size distribution as well as by the exchange cation. Separation of a number of fractions is particularly helpful in making a detailed study of a suspension. A limited amount of work has been conducted on the effects of particle size on specific properties of mud drilling fluids. A knowledge of particle size distribution is essential for a better understanding of fundamental properties of clay suspensions, particularly viscosity and gel strength. The purpose of this investigation was to study the effect of particle size on the viscosity and gel properties of clay suspensions and to determine any changes in mineral composition accompanying variation in size. EXPERIMENTAL PROCEDURE Numerous methods may be used to fractionate a poly-dispersed clay suspension into nearly mono-dispersed systems. Particles larger than 44 micron (325-mesh) may be obtained by wet screening. For sizes from 44 to 1 micron, the fractionation may be accomplished by sedimentation, elutriation plus microscopy,' or turbidimetry.6 When dealing with systems which contain a major portion of particles below l-mi-cron size, slit ultramicroscopy,7 centrifuge methods of Svedberg,5 eams,9 and McBain,l0 and X-ray methods" may be employed. The Sharples super centrifuge has been proved suitable for the economical separation of suspended particles of submicron range.12,13,14 Three-hundred and forty-five gal of 1 per cent by weight Aquagel suspension was mixed in a high-speed 5-gallon mud mixer and the suspension was allowed to stand in 5-gal glass bottles for 30 days to assure full hydration. All particles larger than 44 microns were removed by wet screening. Five fractions in the range of 44 to 1 micron were obtained by sedimentation. The Sharples super centrifuge method described by Hauser and Reed.13 Norton and Speil,14 Ha user and Lynn,15 and Hauser and Schachman,10 as employed to yield five fractions of submicron size. A super centrifuge operation chart prepared by Fancher, Oliphant, and Houssierre12 was used to determine operating conditions for the desired particle ranges. The clay suspension, after removal of all material above 1-micron size, was centrifuged. During rotation of the bowl, the particles were deposited on a thin plastic liner which fit closely inside the bowl. After passing 5 gal of suspension through the centrifuge, the liner was removed and the particles on the liner were scraped off, remixed and recentrifuged. This was repeated five times. Thus, Fractions H, I, K, and L were obtained. The finest fraction, M, remained in an approximately 0.4 per cent suspension. Water was evaporated under reduced pressure from this suspension to yield the finest particles. Results of the fractionation are included in Table 1. In order to achieve proper orientation and humidity conditions for X-ray diffraction analysis, the following procedure was employed. The dilute suspensions were placed on glass slides and allowed to dry at room temperature. This was repeated several times. Previous to measurement each sample first was placed in a water desiccator for half an hour and then allowed to stand for 15 minutes at room temperature. thus yielding an equilibrium condition of about 52 per cent relative humidity. The relative humidity of the room in which the X-ray diffraction was carried out was maintained at approximately 50 per cent so that there was no change in the spacings during the X-ray examination. Samples

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

As a result of using copper-containing scrap in the steelmaking process, the copper content of steels has been steadily increasing for years. Consequently the possible role copper may play in the steelmaking process and in the finished product begins to attract the metallurgists' attention. Some time ago one of the present authors forwarded the idea—based on the results of the analysis of nonmetallic inclusions extracted electrolytically from steels—that sulphur in plain carbon steels is distributed mainly between copper and manganese, the amount of iron sulphide being very small; and that, consequently, the problem of copper and that of sulphur in steel cannot be treated separately.' At the time of the publication of the quoted paper little was known about the relative affinities of copper and manganese for sulphur at high temperatures except that at moderate temperatures (below 1000°C) the affinity of manganese for sulphur is much greater. To gather more experimental data on this subject, the present authors undertook the investigation of the equilibrium constants of the reactions: 2Mn(8 or 1) + S2(g) = 2MnS(s) 4Cu(s or 1) + S2(g) = 2Cu2S (S or I)* 2Fe(s) + S2(g) = 2FeS (s or 1) over a range of temperatures wide enough to establish the dependence of these equilibrium constants on temperature. From the equilibrium constants (K = l/Ps2) the free energy of formation (affinity) can be calculated from F° = -RTln 1/PSt (1) where the standard conditions chosen are: 1 atm of sulphur pressure and the activities of condensed components equal one. The decomposition pressure, Ps2, of sulphur over the respective sulphides is too small to be measured directly, but there is a way of eliminating this difficulty by measuring the equilibrium constant of the reaction between the sulphide and hydrogen. From the latter and from the equilibrium constant of the thermal dissociation of H2S we then calculate Ps2 for the respective sulphide. 2Mn + 2H2S = 2MnS + 2H, 2H2 + S2 = 2H2S_________ 2Mn + S2 = 2MnS The numerical values of the equilibrium constant of the thermal dissociation of H2S at different temperatures were taken from Kelley's paper, "The Thermodynamic Properties of Sulfur and its Inorganic Compounds."² In previous experimental work published by Jellinek and Zakowski3 and by Britzke and Kapustinsky4 the equilibrium constants of the reactions Metal sulphide + H2 = H2S + metal were determined by passing hydrogen, at different rates of flow, over the sulphide, analyzing the resulting H2S + H2 mixture and then extrapolating the H2S/H2 ratio (which is a function of the rate of flow) to the zero speed of flow, a method necessarily involving considerable uncertainty. In the present work the equilibrium ratio was actually measured instead of being extrapolated. The apparatus is shown in Fig 1. Experimental Procedure The sulphides were prepared by the following methods: FeS Powdered iron which had been reduced with hydrogen (ferrum reduc-tum) was mixed in stoichiometric ratio with sublimed sulphur and carefully ground. The mixture was put into an alundum crucible, covered with pure sulphur, and the reaction started by touching the mixture with a glowing iron rod. After the reaction was completed the product (still containing some metallic iron) was again ground with sulphur, put into a Rose crucible, covered with sulphur, and heated in a strong current of pure hydrogen. Analysis of the final product showed 62.46 pct Fe and 36.59 pct S. Theoretical for FeS: 63.53 pct Fe and 36.47 pct S. MnS Manganese sulphide (precipitated and carefully washed with distilled water containing H2S) was dried in a Rose crucible in an atmosphere of H2S and heated in a current of hydrogen for 2 hr at red heat. The product was then ground and ignited for several hours at 1000°C in a current of hydrogen sulphide. Analysis showed 64.53 pct Mn and 36.63 pct S. Theoretical: 63.15 pct Mn and 36.85 pct S. Some MnS samples were prepared from metallic manganese and sublimed sulphur by mixing and grinding them and then heating in a current of hydrogen sulphide in an alundum tube.

Jan 1, 1950

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By W. F. Rogers, J. A. Stewart, P. J. Kalish, E. O. Bennett

Detailed descriptions are given of materials, apparatus and the experimental procedure used to study the effect of bacteria on sandstone permeability. The factors affecting permeability during injection of bacterial suspensions which have been investigated are: (I) concentration of bacteria; (2) core permeability and median pore size; (3) species of bacteria, mode of aggregation and relative size; (4) injection rate or pressure differential; (5) mean pressure; and (6) depth of penetration of bacteria. The investigation demonstrated that bacteria cannot reduce core pertneability to zero and that their effect on permeability is subject to definite limitations. Remedial or permeability restoration studies also were made. Acidization in combination with reverse flow war found to be an effective method for restoring permeability In cores partially plugged with bacteria. The relationship between the bacterial quantities in the laboratory tests and those found in field operations is discussed. The linear laboratory flow data have been translated into terms of field radial systems; these data indicate the most practical methods of maintaining injection rates in the presence of bacteria are to increase injection pressures or hydraulically fracture the formation. INTRODUCTION It has long been known that various bacteria flourish in the above-ground components of oil field water-injection systems. The presence of these bacteria has led to the suspicion that they might enter into the causes for reduction of injection well permeability, but only recently has an attempt been made to describe the effects quantitatively.1 Biocides are used in many cases without a firm knowledge as to whether the bacteria are killed, or if they are, whether the dead cells affect formation permeability. This project was undertaken as part of a study to determine the effect of bacteria, residual oil and precipitated solids such as iron sulfide or calcium carbonate on the permeability of sandstones and to learn whether any of these materials adversely affect brine injectivity in secondary recovery or disposal operations. This report deals with that portion relating to the effect of bacteria. MATERIALS CORES Three different permeability ranges of Berea sandstone cores were used in the study. The range of initial, absolute brine permeabilities kj were: high — 278 to 400 md: medium—130 to 162 md; and low—17.7 to 48.3 md. The permeability data for the cores used in the tests are included in Table 1. All cores were cut to a nominal 1 in. diameter. Following air permeability determinations, they were molded with an epoxy resin in 1.5 in. ID aluminum sleeves. The sleeves had drilled and tapped holes for intermediate pressure connections along the length of the cores. After molding, the high- and medium-permeability cores were trimmed to 4 in. in length and the low-permeability cores to 2 in. These lengths resulted in pore volumes of approximately 10.9, 10.4 and 4.4 ml, respectively, for the high-, medium- and low-permeability cores. Pressure-transmitting channels were drilled through the plastic into the core proper, using the sleeve holes as drill guides. Width and depth of channel penetration into the core proper were approximately 0.03 in. and 0.05 in., respectively. Three pressure taps were used with all cores; for the high- and medium-permeability cores the taps were spaced 1 in. apart; for the low-permeability cores the taps were spaced 0.4, 0.8 and 1.2 in. from the inlet end. Pore size distributions were calculated from restored-state capillary pressure curves for representative cores in each of the three permeability ranges. In each case the pore size range with the greatest percentage of the pore space included the very small pores up to 0.5 micron in radius. The median pore radii were in the 5.5 to 6 micron range for the high-permeability cores; in the 4.5 to 5 micron range for the medium-permeability cores; and in the 3.5 to 4 micron range for the low-permeability cores.

Jan 1, 1965

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By J. S. Bowles

THE martensite transformation in lithium, dis- covered by Barrett,' has been studied extensively by X-ray techniques by Barrett and Trautz,² and Barrett and Clifton.V he present paper reports the results of an investigation into the metallographic characteristics of lithium martensite. Such an investigation has not been carried out before. The spontaneous transformation in lithium consists of a change from a body-centered cubic to a close-packed hexagonal structure with the hexagonal layers in imperfect stacking sequence." As far as is known at present, this transformation can be regarded as being crystallographically equivalent to the body-centered cubic to close-packed hexagonal transformation that occurs in zirconium,5 although stacking errors have not been reported in zirconium. From a study of the orientation relationships in zirconium, Burgers5 as proposed that the martensite transformation, b.c.c. to c.p.h., occurs by a heterogeneous shear on the system (112) [111]. The crystal-lographic principle underlying this proposal is that the configuration of atoms in the (112) plane of a b.c.c. structure is exactly the same as that in the (1010) plane of a close-packed hexagonal structure based on the same atomic radius. The pattern in 2v2 both these planes is a rectangle d X 2v2d where v3 d is the atomic diameter. Thus a close-packed hexagonal structure can be built up from a body-centered cubic structure by displacing the (112) planes relative to each other.* This mechanism leads to orientations that can be described by the relations: (110)b.c.e. // (0001)c,p.h.; [111]b.c.c. // [1120]c.p.h Observations confirm these relations. In zirconium, Burgers' measurements indicated an angle of 0" to 2" between the close-packed directions, while Barrett's measurements on lithium indicated an angle of 3". According to the Burgers' mechanism, the martensite habit plane for this transformation would be expected to be the (112)b.c.c. plane, for this plane would not be distorted by the transformation. One of the purposes of this investigation was to find out whether the observed lithium habit plane agrees with this prediction of the Burgers' mechanism. Experimental Procedure Materials: The lithium was from the same purified ingot used by Barrett and Trautz.² The Bridgman technique was used to produce single crystals. To maintain a temperature gradient in the melt, during the production of these crystals, it was necessary to use a steel mould with a wall thickness of only 0.015 in. Metallographic Techniques: Lithium specimens could be given an excellent metallographic polish by swabbing them gently with cold methyl or ethyl alcohol.? The best results were obtained with methyl alcohol saturated with the reaction product, lithium alcoholate. With higher alcohols the reaction became progressively slower and the attack became an etch pit attack rather than a polish attack. Butyl and amyl alcohols were used for macroetching. After polishing, it was necessary to remove all traces of alcohol from the specimens; otherwise, on subsequent quenching in liquid nitrogen, the alcohol froze to a glassy film. The alcohol was removed with dry benzene. The benzene in turn had to be removed before quenching, but since it does not react with lithium it could be allowed to evaporate. The specimens could then be quickly quenched before they began to tarnish. This operation could be carried out in air on all but excessively humid days when it was advisable to use an atmosphere of dry nitrogen or argon. For examinations at room temperature, the specimens could be transferred directly from the benzene bath into a bath of mineral oil. In mineral oil the specimens oxidized slowly by the diffusion of oxygen through the oil but the structure remained visible for about an hour. Lithium Martensite: Specimens prepared in the manner described above transformed spontaneously to martensite with an audible click when quenched into liquid nitrogen; i.e., M, was above the boiling point of nitrogen (77°K). The disparity between this result and the M, temperature of 71°K, found by Barrett and Trautz, is probably to be attributed to the large grain size and freedom from mechanical deformation of the specimens used in the present work. The relief effects produced by the transformation did not disappear when specimens were quenched from liquid nitrogen into mineral oil at room temperature. This permitted the microstructures to be studied at room temperature where, of course, the martensitic phase was no longer present. Typical micrographs of lithium "martensite" made at room temperature are reproduced in figs. 1, 2, and 3. As anticipated by Barrett and Trautz, the microstruc-

Jan 1, 1952

By A. J. Griest, P. D. Frost, J. R. Doig

During the past 5 years, research directed toward the development of titanium alloys having improved strength-ductility relationships and heat treatability has been carried out at Battelle for the U. S. Air Force.1"3 In the course of this work, a method of heat treating ß-stabilized titanium alloys was developed which produced a wide range of useful properties.4 The heat treatment consisted of two steps: a) solution treating at temperatures in the a-ß phase region, and b) overaging at a lower temperature in the range 800°to 1100°F. Corollary to the alloy development work, research was conducted on the mechanism of the heat-treatment reaction. The investigations of Frost and co-workers on isothermal transformation in Ti-Cr5 and Ti-Mn8 alloys disclosed the existence of the transition phase, w, during the course of the decomposition of metastable ß phase. Subsequent work at Battelle7,8 'and at Case Institute by Brotzen and co-workerss further clarified the nature of the decomposition process. Beta decomposition was found to proceed by the following series of reactions: 1 2 3 4 a + Ti, My (in eutectoid systems). ßo, ßr, and ßU refer to ß phase of original, enriched, and ultimate alloy contents, respectively. Omega is a transition phase having a complex structure. 10-13 Step 4, of course, occurs only in ß-eutectoid systems. This paper presents data correlating transformation behavior with mechanical properties for the following alloys: Ti-8Mn, Ti-8Mn-2A1, Ti-4Mn-4A1, Ti-6Al-4V, and Ti-4Fe. The isothermal decomposition of ß in titanium-manganese alloys of similar composition has been investigated by Frost and coworkers8 and the effect of various annealing treatments on alloys in this system has been studied by Holden, Ogden, and Jaffee.14 The compositions Ti-8Mn-2Al, Ti-4Mn-4A1, and Ti-6A1-4V, were studied in the present work in an effort to define more clearly the effect of aluminum on the response to solution and aging treatments. Ogden, Holden, and Jaffee15 have invesitgated the effect of aluminum on the response of a similar alloy (Ti-8.8Mn-2.46A1) to annealing treatments, and Luini and Lee16 have made an exploratory investigation of the heat-treatability of the Ti-4Mn-4Al alloy. The Ti-4Fe alloy was studied as an example of a moderate1y active eutectoid system. Holden, Ogden, and Jaffee 17 have studied Ti-Fe alloys and have presented some hardness data for aging at 400°C for alloys of Ti-2.56, 5.01, and 7.35 iron after quenching from the a-ß field (750°C). EXPERIMENTAL PROCEDURES The experimental procedures generally used in the precipitation-hardening study are outlined in the following sections. Departures from these techniques are noted in the discussions of the individual alloys. Table I presents the nominal and actual compositions of the alloys studied, together with the swaging and rolling temperatures. In all cases, these temperatures were in the a-ß field and the microstructures consisted of an equiaxed a-ß mixture. Melting and Fabrication—Except for the commer-

Jan 1, 1960

By F. G. Tahmoush, N. J. Grant, E. P. Abrahamson

The effect of grain size on the brittle -ductile transition temperature of pure iron and three dilute Fe-W alloys has been investigated by slow bend tests. The brittle-ductile transition temperature for pure iron increased with increasing grain sizes from 8000 to 500 grains per sq mm where the transition temperature then decreased with further increase in grain size. The dilute additions of tungsten lowered the transition temperature for fine grain sizes, suppressed a reversal of the curve in the coarse grained portion, and raised the transition temperature for this region. The frequency of twin occurrence increased with increasing grain size and decreasing temperature. The object of the present investigation was to re-examine the effect of grain size on the brittle -ductile transition of pure iron and several dilute Fe-W alloys. Current literature normally presents a simple relationship between grain size and the brittle-ductile transition temperature, namely, that the transition temperature increases with increasing grain size. Heslop and etch' have studied the transition temperature of mild steel by V-notch Charpy impact tests for the grain size range between 200 and 6000 grains per sq mm. The result was a linear plot of In 1-1/2 vs brittle-ductile transition temperature, where 1 is the grain diameter. Recent experiments by sipos2 revealed the possibility of a reversal in the slope of the grain size vs transition temperature plot for pure iron; however, his investigation was limited in scope, and the data obtained were insufficient to permit a definitive curve. The present investigation was undertaken in an effort to confirm or extend the grain size effect observed in iron by Sipos. PROCEDURE All alloys were vacuum induction melted, using 99.95 pct Fe containing 0.03 pct 0 and 0.004 pct C. Four ingots were made, ranging from pure iron to iron with 0.035 pct W. The chemical composition of each alloy, after processing, is given in Table I. The four alloys were prepared as 45 lb heats and cast into 4 in. diam by 16 in. molds. They were then extruded into 3/4 in. rods at 1800oF. Specimens for chemical analysis, taken from various positions along the rods, revealed no variation in tungsten content along the length. The extruded rods were reduced to 0.156 in. diam stock by a series of cold swaging operations involving intermediate vacuum annealing treatments. This procedure yielded a final cold reduction in area ranging from 10 to 90 pct. The swaged rods were chemically cleaned, cold pressed to a cross section of 0.10 by 0.18 by 1.0 in. long (2.54 by 4.73 by 25 mm). The specimens were wrapped in iron foil and vacuum sealed (10-4 mm Hg) in quartz. Various heat treatments at temperatures from 700" to 1300oC were utilized to produce grain sizes from 8000 to 1 grain per sq mm. Grain sizes were determined by measuring the average area of grains in a polished section. In specimens with grain size greater than 20 grains per sq mm, the total number of grains in the cross section was counted and then divided by the area to yield grains per sq mm. Grain size was measured both for longitudinal and transverse cross sections. The average of the two measurements was plotted vs transition temperature. An Instron Table Model testing machine was used to determine the transition temperature of specimens tested in three point horizontal bending. The specimen was supported by two 1/4 in. dowels one in. apart. Bending was accomplished with a push rod, the end of which had an 1/8 in. radius. The head speed was 50 in. per min. Temperatures were established through the use

Jan 1, 1963

By G. R. Smithson, John E. Hanway

This paper, the first of two papers covering the development of a metallurgical process for the treatment of a complex ore, describes the bench-scale experimental Program undertaken as a basis for initial process design. The results of using various potentially applicable process steps are detailed and the basis for selecting certain of these steps for Pilot-plant development is outlined. A process consisting of the steps of sulfate roasting, leaching, copper recovery, solution purification, zinc electrolysis, and brine leaching for lead recovery was recommended for further study. THIS paper describes the bench-scale development of a sulfate roasting process designed to recover copper, lead, and zinc from a complex ore. The extrapolation of the bench-scale results to pilot-plant design and the results of pilot-plant operation will be described by Lund, et al.' in a subsequent paper. Several years ago, the research divisions of the St. Joseph Lead Co. became responsible for the development of a metallurgical procedure to treat a complex sulfide ore containing copper, zinc, and lead sulfides. The primary objective was to devise a procedure which would permit economic recovery of the nonferrous values. As could logically be expected, the study of conventional flotation procedures was undertaken; in addition, however, because the physical nature of the mineral association in the complex ore indicated that physical methods of ore beneficiation might not prove to be entirely satisfactory, a program also was established to investigate alternative methods of direct metallurgical treatment for recovery of the metal values. Exploratory test work by the St. Joseph Lead staff led to the conclusion that a sulfate roasting technique represented the most attractive approach for a direct metallurgical process. Sulfate roasting would provide for the selective conversion of the nonferrous values to forms soluble in conventiona1.1 leaching agents and would permit their efficient separation from the insoluble iron and other gangue materials. It should allow efficient utilization of the thermal energy available from oxidation of the sulfide raw material, and might provide an opportunity for recovering byproducts such as iron and sulfur. The decision to evaluate a selective sulfation procedure as a basic processing step also was influenced by the excellent results obtained by the St. Joseph Lead Co. in using this procedure for the recovery of cadmium from zinc sulfide concentrates. The choice of selective sulfation as a major processing step served as a basis for an extended experimental investigation of the process with bench- and pilot-scale equipment to prove its feasibility. St Joseph Lead Co., aware that Battelle Memorial 1nstitute had participated in the development of several fluidized-bed sulfate roasting procedures, asked Battelle to undertake the bench-scale development of a suitable sulfation process. This paper describes the procedure used and the results obtained at Battelle in the treatment of the complex sulfide ore. EXPERIMENTAL WORK Nature of the Raw Material. The sulfide ore deposits of interest are essentially a massive sulfide, with the indivudual ore minerals being extremely fine grained and intimately intergrown with each other and with the associated gangue. The zinc in the ore is present mainly as sphalerite (ZnS), the lead as galena (PbS), and the iron either as pyrite (Fes2) or as pyrrhotite (FeS). Table I shows the chemical analysis of various individual samples of the ore. These analyses illustrate the variability of the ore body and impose a rather severe requirement on any type of metallurgical process—that of being able to tolerate probable wide variations in the assay of the head ore. The tentative flowsheet designed to serve as a guide for the initial experimental investigation of

Jan 1, 1962

By W. S. Hyler, W. L. Bruckart

The powder metallurgy and arc-cast types of wrought molybdenum stock were studied in rotating beam fatigue. Endurance ratios of unnotched specimens after 5x10 cycles were found to be 0.74 and 0.81, respectively. Fatigue notch factors (K,) of 1.36 and 2.05, respectively, were obtained on V-notched specimens having a theoretical stress-concentration factor Kt = 3.1. MOLYBDENUM and its alloys are rapidly gaining importance as engineering materials of construction for high temperature applications. AS a wrought material, molybdenum and its alloys are outstanding above 1800°F. It is necessary, however, with molybdenum to provide elevated temperature oxidation protection. This is currently being studied by a number of investigators. Thus far, there have been no published data on the fatigue behavior of molybdenum either at room temperature or at elevated temperature. The knowledge of fatigue behavior, particularly notched fatigue behavior, becomes increasingly important as the engineering importance of a material increases, especially from the design standpoint. The work described here was directed toward determination of the notched and unnotched rotating beam fatigue characteristics of molybdenum at room temperature. Also, it was desired to learn whether any difference exists between wrought molybdenum of the powder metallurgy and the are-cast types. Fabrication History of Bar Stock For this work, bar stock was procured from Climax Molybdenum Co. (are-cast type) and from Westing-house Electric Corp. (powder metallurgy type). The processing histories of these materials are listed in Table I. The first lot of are-cast molybdenum was deoxidized by aluminum additions. The second lot was deoxidized by carbon." Both lots of the powder Microstructure A microscopic examination of these materials, as received, revealed the powder metallurgy molybdenum to be free of inclusions and to be finely fibered. On the other hand, the are-cast C molybdenum possessed numerous carbide inclusions, and the arc-cast A appeared to have coarse grained fibers. These are shown in Fig. 1. Owing to the large apparent difference in fineness of fiber between the are-cast A and the powder product and are-cast C, a check was made of the recrystallized grain sizes to determine whether these differences persisted. A series of recrystallization anneals revealed mixed grain sizes in both the are-cast A and the powder product. Variations in grain diameter of as much as 50 times were found after full recrystallization at 1200°C for 30 min. There was no distinction between the two. Arc-cast C was not checked. Room Temperature Mechanical Properties Prior to subjecting the materials to fatigue tests, room temperature mechanical properties were determined. These data, together with the tensil: strength of the notched bars, data,togetherare listed in Table tensil: There were no significant differences in the tensile strengths of the two types of molybdenum. However, the powder metallurgy material was generally more ductile and yielded at a somewhat lower stress than the arc-cast material. Tensile strengths of the notched specimens indicated a slightly greater notch strengthening effect in the are-cast C than in the powder product, lot 2. Room Temperature Fatigue Properties Sample Preparation: Specimens were prepared for use in R. R. Moore rotating beam fatigue machines. These specimens had a continuous radius test section with a minimum diameter of 0.260 in. The specimens were prepared by grinding to shape and polishing to produce a smooth unworked surface. Polishing consisted of rotating a disk in the continuous radius section on which were attached, successively, emery belts of 240, 400, and 600 grit. The specimens were slowly rotated during the operation. The belt speed was high, and rotation was such that polishing scratches were longitudinal. Unnotched Fatigue Properties: Unnotched fatigue data were obtained from a number of specimens of each of the four lots of molybdenum. The results of the tests are presented in Fig. 2. From this figure,

Jan 1, 1956

By E. C. W. Perryman

IN spite of the large amount of work which has been carried out on the recrystallization of aluminum and its alloys, there has been no complete investigation of the recrystallization characteristics of A1-Mg alloys. The most complete investigation is that reported by Bungardt and Osswald' who, working with commercial-purity materials, found that the temperature both of beginning and of complete recrystallization increased with magnesium content up to about 2 pct Mg, then decreased with a further increase in magnesium up to 5.0 pct, and thereafter increased again. Michaud and Segolz working with 99.93 pct A1 also found the temperature of beginning of recrystallization to decrease as the magnesium content increased from 2.13 pct to about 4.5 pct. Chossat3 using aluminum of 99.99 pct purity found that 0.12 pct Mg had no effect but that 0.4 pct Mg increased the recrystallization temperature by about 30°C. That no effect was found for 0.12 pct Mg does not agree with the later results reported by Demer and Beck4 who found that 0.025 pct Mg in 99.99 pct A1 increased the time for complete recrystallization and furthermore increased the activation energy for the recrystallization process. Kratz" using 99.997 pct A1 found that 0.5 pct Mg increased both the temperature of beginning and of complete recrystallization by 100°C. Chadwick and Hooper" working with commercial-purity material found that 1 pct Mg increased the temperature of complete recrystallization by about 40 °C for cold reductions in the range 17 to 72 pct. With smaller amounts of cold work produced by stretching (10 pct strain), they found no significant effect of magnesium. The latter result agrees with that obtained by Williams and Eborall' who found no effect of 2 pct Mg on the recrystallization temperature of commercial-purity aluminum strained 10 pct or less by stretching. Experimental Procedure Material Used: The chemical analyses of the materials used throughout this investigation are given in Table I. Fabrication: The alloys were cast in iron molds which had been washed thoroughly with alumina. After scalping, the ingots were annealed for 16 hr at 450°C, pressed, annealed at 450°C for 16 hr and hot rolled to 0.25 in. After hot rolling, the slabs were alternately annealed and cold rolled to 0.036 in. Cold-rolling reductions between intermediate anneals were kept at about 30 pct and a high intermediate annealing temperature of 450°C was used so as to obtain, as nearly as possible, similar starting grain sizes for the different materials. All intermediate anneals were done in a salt bath and were followed by cold-water quenching so as to retain all the magnesium in solid solution. The final cold reductions investigated were 20, 30, 40, 50, 60, and 80 pct. The initial grain sizes, that is, the grain size before the final cold reduction, were all very similar. Annealing Procedure: Specimens, 1 in. sq, were cut from the 0.036 in. sheet and annealed in a salt bath, the temperature of which was controlled to k2"C. Separate specimens were annealed for different times at 350°, 375", 400°, and in one or two cases at 415°C and after annealing were quenched in cold water. The time taken for a specimen to reach temperature was approximately 5 sec. Metal-lographic examination after annealing showed that no precipitation of Mg+413 occurred during cooling. Procedures Used for Determining Recrystallization Characteristics: All specimens were electrolyti-cally polished and etched by the method described previously1° and polishing was continued until about 0.002 in. had been removed from each side of the specimen. Using this technique, the smallest recrys-tallized grain which could be observed with cer-

Jan 1, 1956

By S. J. Matas, R. F. Hehemann, R. H. Goodenow

The hot-stage metallographic method has been employed to determine radial growth rates of upper and lower bainite. Lower bainite appears to grow as individual plates that increase in both length and thickness while upper bainite grows as sheaves of closely spaced plates or needles. A discontinuity in the temperature dependence of the growth rate appears to be associated with the transition from upper to lower bainite and stepped quenching experiments suggest that lower bainite will not continue to grow when the temperature is raised to the upper range. Thus, a single process does not appear to control the growth of both upper and lower bainite. A tentative model based on the forces acting on a dislocation interface is proposed to account for the slow growth of bainite. It has been recognized since the early studies of Davenport and Bain that a close relationship exists between the martensite and bainite transformations in steels. However, diffusion of carbon during the transformation has lead to considerable controversy concerning the reaction mechanism.1-7 Many studies4,5,7-9 have emphasized the structura and kinetic aspects of the bainite reaction and, in particular, the difference observed between the two forms of bainite—frequently termed upper and lower bainite. A kinetic difference between the two types of bainite has been revealed in the activation energy determined from the overall reaction;4,5 however, many difficulties arise in an interpretation of these activation energies since a number of temperature dependent factors contribute to the kinetics of the overall reaction. The displacive surface relief10 accompanying the bainite reaction permits a separation of the nuclea-tion and growth contributions to the reaction and allows the kinetics of the growth process to be examined. Several investigations of this type have been conducted; however, they have been restricted to the low temperature range.3'6'11 Here, bainite plates are observed to grow slowly in both length and width. The present investigation extends such studies to include the upper bainite range. MATERIALS AND PROCEDURE Materials. The composition of the steels studied in this investigation are presented in Table I. The range of composition permitted a study of the effect of carbon content on the growth rate of upper bainite in the 9 pct Ni steels and consideration of both upper and lower bainite in the higher carbon steels. These steels were received as hot-rolled rounds and were forged to approximately 1/2 in. thick plates for preparation of metallographic specimens. In order to produce an essentially zero carbon steel, Steel A was decarburized in wet hydrogen at 1550°F for 15 days with the result tabulated as Steel AD. Experimental Procedure. In order to study the slow growth of the displacive transformation product, a commercially available Leitz hot stage was modified to permit heating of the specimen by its own resistance in a manner similar to that employed by other investigators.6 The furnace chamber was maintained at a pressure of 2 to 3 X 10-5 mm Hg prior to austenitizing at 2000° ± 12° F for 5 min. Samples could be cooled from the austenitizing to the transformation temperature in approximately 15 sec and the progress of transformation was recorded with a 9 cm by 12 cm single frame camera or a 16 mm movie camera. RESULTS AND DISCUSSION Growth Characteristics. The general growth characteristics observed in this investigation were analogous to those reported previously.3,6,11 Typical growth sequences for the high temperature and low temperature forms are illustrated in Figs. 1 to 5. In both temperature ranges, bainite plates increase in length at slow, temperature dependent rates until interrupted by a grain boundary, another plate, or

Jan 1, 1963

By S. A. Spachner

An analysis of the powder patterns of the omega transition phase in three binary titanium alloys containing 8 pct Cr, 13 pet Mo, and 15 pet V, respectively, showed that all could be indexed on an orthorhombic unit cell. The unit-cell dimensions were all quite similar. There is evidence for the occurrence of more than one transition phase in Ti-Cr and Ti-V alloys. FOLLOWING the discovery of a new brittle phase in certain titanium-chromium alloys by Frost, Parris, Hirsch, Doig, and Schwartz,' named ? by these investigators, much interest has developed concerning the identification of alloy systems in which this phase exists, kinetics of the transformation in such systems, and the crystal structure of the ? phases appearing. Omega has been found in alloys of titanium-manganese, titanium-molybdenum, titanium-iron,' and titanium-vanadium.' In the present work, a study was made of the powder patterns of the ? phase occurring in alloys of Ti-8Cr, Ti-13Mo and Ti-15V in an effort to obtain a basis of comparison for ? phases appearing in these different alloys. Comparison of Alloys for ?-Phases Two hundred mesh powders of Ti-8Cr, Ti-13Mo and Ti-15V were prepared. A portion of powder sufficient for three x-ray powder specimens was placed in a Vycor tube, evacuated to less than 0.1 µ pressure, filled with argon, and sealed. The tubes were then heated to 900°C, held at this temperature for 30 min, and water-quenched. Following this transformation to the ß phase, the specimens were quenched in lead or solder pots, held at the desired temperature for varying lengths of time and water-quenched. The heat-treatments used and the phases identified are listed in Table I. The intermediate water quench was used in lieu of direct downquenching from 900°C to the bath temperature desired to circumvent the possibility of transformation of the powder specimen from ß to (ß + a) while it was being moved from the homog-enization furnace to the lead bath. To check the possibility that upquenching to the bath temperature might bring into play a different mechanism than downquenching to this temperature, resistivity measurements were compared on Ti-8Cr rod specimens which were transformed isothermally at 400°C by downquenching from the solution-treatment temperature and those which were transformed at 400" C by upquenching ß specimens from room temperature. The results are shown in Fig. 1. No difference in transformation mechanism was noted. It soon became apparent that sufficiently detailed Debye-Scherrer photograms of the ? phase in the alloys which were to be used could not be obtained by the use of copper radiation. Although satisfactory photograms of ß and ß + a phases were obtained with this radiation, the ? phase appeared to exhibit mild fluorescence, making interplanar spacing computation virtually impossible. Molybdenum radiation appeared to offer promise in cutting down this fluorescent effect, the mass absorption of titanium for molybdenum radiation being 23.7 in contrast to 204 for copper radiation. The reduction in the accuracy in determining the location of the photo-gram lines caused by the shorter wave length of molybdenum characteristic radiation did not appear to be a significant factor. Utilizing a camera of 57.3 mm radius, best results were obtained for exposure times ranging between 30 and 40 hr. Tube potential

Jan 1, 1959

By John L. Walter

A sintered compact of iron containing 0.007 vol fraction of glass , prepared 6). powder rnetullurgtcal lechniques, was rolled lo foil, 0.001 in. /hick. The foil sullrples were anneuled a1 650° to 850°C in hydrogen. Pri,narj recryslullization prodtnced large grains which Lc3ere highly elongnled in the rolling direclion und which had an unusual prgferred orientation. The glass parlicles assumed a stringerlike dispersiorz on working; llie slrinyers were parallel lo the rolling direction and to the long axis of the grains. The same unusual grain structure, preferred orientation, and stringerlike dispersion of purticles are found in heal-ily rolled and annealed foil of tungsten which has heen doped wilh small amounts of aluminum, silicon, and polassiutvt. Both the proper dispersion of the particles and severe working (reductions in excess of 98 pct) are necessary to produce the elongzcted grain structure. RECENTLY, the author reported on the origin of the elongated or "nonsag" grain structure in tungsten foil which was doped with aluminum, silicon, and potassium.' It was observed that particles, identified as mullite (Al6Si2Ol3), were present in the doped ingot (as sintered) and at all stages of processing from ingot to sheet or wire. It was shown that the particles, being plastic at tungsten working temperatures (up to 1550"C), underwent a "stringing out" parallel to the working di-direction. It was concluded that these strings of particles were responsible for the formation of the highly elongated interlocking grains observed in doped tungsten wire or sheet. To give further credence to this explanation of a long-observed but not understood phenomenon, it was decided to design a new system, one which was analogous to the doped-tungsten system. Thus, a bcc metal, iron, was chosen to be doped with glass which would be plastic at reasonable working temperatures for iron. The glass chosen was a #0080 Corning lime glass which melts at about 810°C. This is approximately the same fraction of the melting point of iron (0.6) as the melting temperature of mullite is of tungsten. It will be shown that all the observed unusual features of the doped tungsten are duplicated in the glass. doped iron, even to the preferred orientation of the grains in the recrystallized sheet. In the tungsten sheet the preferred orientation consists of two components, (1i3)(691) and (013)(362), neither of which has been observed as a component in textures of primary recrystallized bcc metals. EXPERIMENTAL PROCEDURE The glass, in the form of fine powder, was added to high-purity electrolytic iron powder and mixed dry. The particular composition chosen was 0.007 vol fraction of glass. After mixing, the powder was mechanically pressed to a disk 0.5 in. diam and 0.15 in. thick at a pressure of 5000 psi. The pellet was sintered, in pure dry hydrogen, for 2 hr at 8 50°C. The sintered pellet was then heated to 750°C and rolled to 50 pct reduction of thickness in two passes, with reheating between passes. The rolling temperature was then reduced to 600°C and the slab was rolled to a thickness of 0.050 in. Rolling to 0.010 in. was accomplished in several passes at 300°C. Final reductions to 0.003 and 0.001 in. were taken at room temperature. This rolling temperature schedule was similar, in terms of the fraction of the melting point, to that used in the rolling of the doped tungsten. The total reduction of thickness was in excess of 99 pct. Samples of the rolled foil were lightly electro-polished and annealed for 1 to 6 hr at temperatures of 650" to 85O°C in hydrogen. Samples for transmission electron microscopy were thinned on a Disa Electropol using AC-1 electrolyte.

Jan 1, 1968

By S. Kado, G. Derge, L. Yang

Self-diffusion coefficients of silver in molten silver have been measured by means of the capillary-reservoir method in the temperature range 1002" to 1105°C. The results can be .represented by the equation D = (7.10 i 0.06) X 10-4 exp [(—8150 ± 1130)/RT]. The heat of activation agrees within the limit of experimental uncertainty with that for the viscous flow. The validity of the Eyring and the Stokes-Einstein equations are examined on the basis of the self-diffusion coefficients obtained and the known viscosity data of molten silver. MEASUREMENT of the self-diffusion coefficient of silver in molten silver was made in the temperature range 1275° to 1378°K, using the capillary-reservoir method and &"' as the radioactive tracer. The experimental arrangement is shown in Fig. 1. Silver of 99.99 pct purity (fine silver), was melted and degassed in vacuum in a graphite crucible situated inside a McDanel vacuum jacket. The crucible (4 in. tall and 1 in. ID) was protected both at the top and at the bottom with graphite shields and contained about 220 g of silver. The sample holder was a piece of graphite rod (1 in. long and 1/2 in. diam) with 4 capillaries drilled longitudinally into it. The holder was screwed onto a long graphite rod (12 in. long and 74 in. diam) which was connected to a steel disk hanging on a nylon string through a glass pulley. The steel disk kept the sample holder at the center of the McDanel tube and was heavy enough to overcome the buoyancy when the holder was lowered into the molten silver. By turning a handle connected to the pulley through a tapered glass joint, it was possible to raise or lower the sample holder without breaking the vacuum. Two such arrangements were constructed, sitting side by side in 2 Kanthal furnaces. One with non-radioactive silver in its crucible was used for the diffusion run and the other with radioactive silver in its crucible was used for filling the capillaries. To fill the capillaries with radioactive silver, the sample holder was degassed first and then lowered into the radioactive molten silver in vacuum. Purified argon gas was then admitted into the system to push the liquid silver into the capillaries. After cooling in argon, the filled capillaries were polished on emery paper to expose the top of the rod and used immediately as samples for the diffusion run which was carried out at the same temperature as that used for filling the capillaries. During the diffusion run, the samples were degassed in vacuum and lowered slowly into the nonradioactive molten silver before purified argon was admitted into the system. After a predetermined period of time, the samples were raised out of the melt and cooled in argon. The temperature of the melt was measured before and after the run with a chromel-alumel thermocouple inside a McDanel protection tube. Another chromel-alumel thermocouple attached to the outside wall of the McDanel vacuum jacket was used to indicate any fluctuation in the temperature of the furnace during the run, which was found to be less than ± 2°C for the longest run made (93 min). The temperature gradient inside the molten silver was found to be negligible. No significant difference was observed in the results obtained whether the melt was stagnant during the run or was stirred by raising and lowering the sample holder slowly a few times a minute for a distance of about 1/4 in. inside the melt.

Jan 1, 1959

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964

By A. D. Schwope, L. R. Jackson, A. M. Hall

IN the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of recrystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. MATERIALS USED IN THE INVESTIGATION Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table 1. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871°C in air and hot rolled to 3/8 in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hrs. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pct reduction) in 6 passes and annealing at 427°C for 4 hrs. This annealed wire was then drawn to 0.081 in. wire, (37.1 pct reduction) in 2 passes. Square rod was made by hot rolling wire bars to 9/16 in, rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 3 1/2 hrs at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°C for 3 1/2 hrs. Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 X 0.268 in. square, annealing for 332 hrs at 538°C and cold rolling to 0.257 X 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hrs in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from 0.015-0.025 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. EFFECT OF COLD DRAWING AND TENSILE STRAIN ON STRENGTH OF COPPER Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are

Jan 1, 1947

By Robert Y. Grant

This study outlines the history of metal mining in Japan and the characteristics of the industry as they existed from 1925 to 1945. Mining and milling operations are described together with the role of the Japanese Government. A description of post-hostilities conditions and the present state of the industry is included. MANY of Japan&apos;s larger and better known mines date back to the early centuries of the Christian Era. The first stimulus to mining in Japan came through the growth of Buddhism, A. D. 600 to 700, and the attendant need for copper and other metals for temple ornaments and statues. During the Feudal period, 1333 to 1568, mine operations were expanded to meet the demand for ornament metal and for financing of campaigns. After removal of the seat of government from Kyoto to Tokyo, about 1600, the Tokugawa Shogunate placed great emphasis on mining, and many new mines were opened, some of which are still operating. Toward the end of the Tokugawa period, mining had declined sharply from its earlier peak. The easily worked, high grade portions of the orebodies had been exhausted, and the mining techniques then available could not exploit the deeper, lower grade ores. Similarly, extraction of metal from the sulphide ores presented a major problem. With the Meiji Restoration in 1868 and the rapid opening of the country to western ideas came a rejuvenation of the mining industry. Mining, milling, and smelting processes were greatly improved, resulting in the extension of development work into hitherto inaccessible portions of orebodies. The demand for metal during World War I stimulated activity throughout the industry; copper mining, particularly, expanded to a point where Japan ranked second among world producers.* During the depression following the war, mining underwent a severe contraction in activity, recovering slowly during the late 1920&apos;s only to undergo a further setback in the worldwide depression which started in 1929. Mineral output declined in 1930, but the beginning of Japanese expansion, 1931 to 1932, brought about an increase in the output of mine products starting between 1932 to 1934. Production continued to rise, the peak output being attained 1939 to 1943 in virtually all commodities. The greatest production of iron ore, chromite, and manganese was not experienced until 1944 when blocked imports, coupled with strong demands for steel, provided the needed incentive. Through necessity, Japan produced much of her mineral needs from her own mines at high cost during World War 11. Taking the 1932 to 1936 period as an average, however, Japanese mines produced only 16 pct of the iron available to industry, 8 pct of the lead, 33 pct of the zinc, and 68 pct of the copper. Nearly all of Japan&apos;s output of gold, silver, copper, lead, and zinc between 1925 and 1945 came from 30 to 49 pct of the mines for which production data are available; for example, 66 of 174 gold-silver mines accounted for 98 pct of the output of this group. Further analysis of mine output indicates that a large part of Japan&apos;s metal output was derived from a few large mines; about 10 gold-silver, 15 copper, 3 lead-zinc, 5 manganese, and 2 iron mines account for most of the production. Many of these mines have been operated for 200 to 400 years. With the

Jan 1, 1952

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute&apos;s influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger&apos;s argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.&apos; Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute&apos;s influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute&apos;s influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968