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By S. N. Singh, M. C. Flemings

Results are presented of a detailed study on the combined influences of ingot dendrite am spacing and thermomechanical treatments on the structure and solution kinetics of high --purity cast and worked 7075 alloy. Solution kinetics were found to depend sensitively on ingot dendrite am spacing and on details of therrnomechanical processing, including amount of reduction and extent of&apos; solution treatment before reduction. An approximate analysis is given for rate of solution of nonequilibrium second phase in the cast and worked structres; results of the analysis are compared with experiment. MICROSEGREGATION in high strength aluminum alloys manifests itself as "coring" (composition differences within the primary aluminum-rich phase), and as interdendritic second phase. The mechanism of formation of the microsegregation is understood, and approximate prediction of the amount of second phase is possible for simple binary systems.1,2 When alloy elements or impurities are present in amounts less than their solid solubility at solution temperature, any phases forming from these elements are termed "nonequilibrium" and can be dissolved by appropriate solution treatment. The rate at which the nonequilibrium phases are removed depends sensitively on their spacing (dendrite arm spacing in the cast material, or band spacing in wrought material). When alloy elements or impurities are present in amounts in excess of their solubility at the solution temperature, second phase particles form an "equilibrium" second phase that does not dissolve in heat treatment and may, in fact, coarsen in such treatment. Usual commercial, high strength, wrought aluminum alloys contain nonequilibrium second phases that were not fully dissolved during ingot processing. They also contain equilibrium second phases resulting from impurities present in amounts greater than their solubility. As has been shown by Antes, Lipson, and Rosenthal,3 and will be demonstrated further in a subsequent paper by the authors,4 significant improvements in mechanical properties of high strength alloys can be achieved by reduction or elimination of these second phases. Methods of elimination are 1) to employ high purity materials to minimize amounts of equilibrium second phase, and 2) to employ suitable thermomechanical processing techniques to fully eliminate nonequilibrium second phases. Work reported herein comprises a study of selected thermomechani- cal processing treatments, and of their influence on solution kinetics of wrought high purity 7075 alloy. EXPERIMENTAL PROCEDURE Melting and Casting. The bulk of the work reported was performed on a single ingot of high purity 7075 alloy. The ingot was 4 in. by 4 in. by 8 in. high, uni-directionally solidified following a procedure previously described.5 The mold was heated to 1350°F before pouring the melt. The bottom chill was carbon coated stainless steel. Water was circulated through the chill after the melt was poured. The 7075 alloy was prepared from high purity virgin material (aluminum, zinc, magnesium) and from master alloys (Al-50 pct Cu, A1-15 pct Cr, A1-5 pct Ti). Final measured melt composition (wt pct) was: Zn Mg Cu Cr Ti Fe Si Al 5.70 2.28 1.35 0.18 0.15 <0.002 <0.012 bal Melting was done in a silicon carbide crucible; all tools were coated with zircon wash to minimize iron contamination; degassing was by bubbling chlorine through the melt. che-rmomechanical Treatments. Detailed studies were made on material taken from a location approximately 13 in. from the chill and 51/2 in. from the chill (i.e., from 1 in. thick slices taken between 1 and 2 in. from the chill and between 5 and 6 in. from the chill). Solution treatment was done at 860°F in an air-circulating furnace with a "bottom drop" arrangement to achieve minimum delay time between solution treatment and quench. Samples solution treated in this way were 2 in. by 2 in. by 1 in. Temperature of the quench water was approximately 10°C. Mechanical reduction was by cold rolling. Samples 11/2 and 51/2 in. from the chill were treated for 12 and 24 hr, respectively, before cold rolling. Reduction by cold rolling was then 4/1, 16/1, and 35/1. In each case, several intermediate anneals (1/2 hr at 860°F) were used to permit reaching the final thickness without cracking; two such anneals were used for the 4/1 reduction, five for 16/1, and six for 35/1. After working, materials were again solution treated for various lengths of time from 0 to 48 hr and quenched in water. Structural Measurements. Secondary dendrite arm spacings were measured using procedures previously described.&apos; For each measurement reported, five photomicrographs were first made at X75. Measurements were made of dendrite arm spacings in at least 20 different grains (grain structure was equiaxed). Grain size measurements were made by running a number of random traverses across photomicrographs of the samples and obtaining the mean lineal intercept. Measurement of the volume percent of second phase and porosity was done by quantitative metallography. A two-dimensional systematic point count was used

Jan 1, 1970

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat&apos; who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E&apos; and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200&apos;C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970

By J. L. Tomlinson, B. D. Lichter

Electrical resistivities 01 liquid Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi alloys were measured using an electrodeless technique. The resistivities ranged from 50 to 160 microhm -cm, temperature dependences were positive, and no sharp peaks in the composition dependence of the resistivity were observed. On the basis of these observations, it was concluded that the alloys are typical metallic liquids. The electron con-cent9,ation was calculated from the measured resis-tizlity and available thermodynamic data using a model which attributes electrical resistivity to scattering by density and composition flzcctuations. A correla-tion was shown between the departure of the electron concentration from a linear combination of the pure component valences and the value of the excess integral molar free energy. Calculation of the temperature dependence of the electrical resistivity showed a need for more detailed thermodynamic data in these systems and led to suggestions for improvement in the concept of residual resistivity in the fluctuation scattering model. THE electrical resistivity of liquid metals provides information regarding interatomic interactions and their effects upon structure. In this experiment an electrodeless technique was used to measure the electrical resistivities of liquid alloys of Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi, and the results were used with thermodynamic data to calculate a parameter which reflects the tendency toward localization of electrons due to compositional ordering. It was found that the resistivities of these alloys are generally metallic in magnitude and temperature dependence. The electrical and thermodynamic properties are discussed in terms of the fluctuation scattering model&apos;22 which supposes that the electrical resistivity arises from scattering due to a static average structure and departures from the average due to fluctuations in density and composition. Further, this model is compared with the pseudopotential scattering model of Ziman et al.3-5 EXPERIMENTAL PROCEDURES Alloy samples were prepared from 99.999 pct pure elements obtained from American Smelting and Refining Company (except tin which was obtained from Consolidated Smelting and Refining Company.) J. L. TOMLINSON, Member AIME, formerly Research Assistant Division of Metallurgical Engineering, University of Washington, Seattle, Wash., is now Physicist, Naval Weapons Center, Corona Laboratories, Corona, Calif. 0. D. LICHTER, Member AIME, is Associate Professor of Materials Science, Department of Materials Science and Engineering, Vanderbilt University, Nashville, Tenn. This work is based on a portion of a thesis submitted by J. L. TOMLINSON to the University of Washington in partial fulfillment of the requirements for the Ph.D. in Metallurgy, 1967. Manuscript submitted May 31, 1968. EMD Weighed portions were sealed inside evacuated silica capsules, melted, and homogenized before the resistivity was measured. The resistivity of a liquid alloy was measured by placing the sample inside a solenoid and noting the change in Q. According to the method of Nyburg and ~ur~ess,~ the resistivity of a cylindrical sample may be determined from the change in resistance of a solenoid measured with a Q meter as T7--5--W =R7JT^ =&apos;Kc-lm(Y) [1] where L, R, and Q = wL/R are the inductance, series resistance, and Q of the solenoid. The subscript s refers to the solenoid with the sample inside; the subscript 0 refers to the empty solenoid. Kc is the ratio of the sample volume to coil volume and y = 2 [bei&apos;0(br)-j ber&apos;o(br)~\ br\_bero(br) +j bei0 (br) expressed with Kelvin functions which are the real and imaginary parts of Bessel functions of the first kind with arguments multiplied by (j)3&apos;2. The argument of the function Y is hr where r is the sample radius and b2 = po~/p, i.e., the permeability of free space times 271 times the frequency divided by the resistivity in rationalized MKS units. Since Eq. [I] cannot be solved explicitly for p, values of Kc. lm(Y) were tabulated at increments of 0.1 in the argument by. A measurement of Q, and Q, determined a value of Kc . lm (Y) and the corresponding value of br could be read from the table. From the known r, uo,, and w, the resistivity, p, was determined. The change in Q was measured after letting the encapsulated Sample reach equilibrium inside a copper wire solenoid. The solenoid was contained in an evacuated vycor tube in order to retard oxidation of the copper while operating at high temperatures and heated inside a 5-sec-tion nichrome tube furnace capable of obtaining 900°C. Temperature was determined with two chromel-alumel thermocouples, one in contact with the solenoid 30 mm above the top of the sample and the other inserted in an axial well at the other end of the solenoid and secured with cement so that the junction was 2 mm below the bottom of the sample. Temperature readings were taken with respect to an ice water bath junction, and the voltage could be estimated to the nearest thousandth of a millivolt. The lower thermocouple was calibrated by observing its voltage and the Q of the coil as the temperature passed through the melting points of samples of indium and tellurium. The upper thermocouple reading was systematically different from the lower thermocouple reflecting the temperature difference due to a displacement of 60 mm axially and 6 mm radially. Calculations show that the gradient over the sample was less than 2 deg. Q was measured by reading a voltage related to Q from a Boonton 260A Q meter with a Hewlett Packard

Jan 1, 1970

By J. H. Swisher, E. O. Fuchs

Rate equations were derived to describe the kinetics of internal oxidation of cylinders and spheres. The derived equations for cylinders were checked experimentally by means of sub scale thickness and electrical conductivity measurements on Cu-Cr alloy wires. The properties of the internally oxidized samples were examined with conductivity applications in mind. It was possible to produce uniform dispersions of Cr2O3 in copper with an initial chromium content as high as 3 wt pct. While electrical conductivities only a few pct less than that of OFHC copper were obtained, the Cr2Os particle size and spacing were too large for effective dispersion hardening. T.HE process of internal oxidation has been used widely in basic studies of the permeability of gases in metals. In a review article, Rapp1 has discussed the principles of internal oxidation in considerable detail. From a technological standpoint, internal oxidation is often considered undesirable, since it is a means by which inclusions can be introduced into an otherwise clean material. Another important aspect of internal oxidation is its use as a means of dispersion hardening a material. Broutman and Krock2 discuss this and other methods for making dispersion hardened alloys. The only internally oxidized material known to the authors which is commercially available is a Cu-BeO alloy.3&apos;4 This alloy is made from Cu-Be alloy powder, using a so-called Rhines pack. It has a tensile strength of 80,000 psi and retains its strength at relatively high temperatures. The objectives of the present study were to derive rate equations for the internal oxidation of cylinders and spheres, to check the derived equations for cylinders experimentally, and to examine the structure and properties of internally oxidized Cu-Cr alloys. The Cu-Cr system was chosen for this study because uniform dispersions are obtainable at high alloy contents, which is a desirable characteristic in dispersion hardened materials. RATE EQUATIONS FOR VARIOUS GEOMETRIES A number of authors5--9 have derived equations to describe internal oxidation kinetics. These derivations differ somewhat in mathematical assumptions and approximations, and all except one of the derivations deal exclusively with the internal oxidation of plates. The exception is a brief treatment of cylindrical and spherical geometries given by Meijering and Druy-vesteyn9 as a part of a comprehensive paper on the general subject of internal oxidation. These authors did not obtain rate data to check their derivations, although they did show that the hardness profile across an internally oxidized sample is directly related to the rate of interface movement. For cylindrical and spherical geometries, a quasi-steady-state approximation is needed to circumvent mathematical complications in obtaining a solution to the basic differential equations. In using this approximation, we consider the concentration gradient of dissolved oxygen in the internally oxidized zone or sub-scale to be the same as the gradient which would be present if there were no movement of the subscale interface. The steady-state approximation introduces an error of about 1 pct in computing the rate of internal oxidation of an Fe-1.0 pct Mn alloy plate, if the present method is compared to the more exact method of Wagner.7&apos;10 The details of the derivations of the rate equations for cylinders and spheres are given in the Appendix, and only the results of these derivations are given below. The final equations obtained by Meijering and Druyvesteyn9 can be shown to be equivalent to our Eqs. [1] and [2], although the two approaches are somewhat different. Cylindrical Geometry. [2] where r1 is the outer radius of the cylinder or sphere, cm, r2 is the radius of the unreacted core, cm, see Fig. l(a), D is the diffusion coefficient of oxygen in copper, cm2 per sec, %O is the concentration of dissolved oxygen at the surface of the specimen, wt pct, %Cr is the initial chromium concentration in the alloy, wt pct, and t is the reaction time, sec. Plate Geometry. The analogous rate equation for a plate has been derived previously for internal oxidation of Fe-Al alloys.8&apos;11 For Cu-Cr alloys, we may write the same equation as follows: [3] where r1 is the half-thickness of the plate, cm, and r2 is the distance from the mid-plane to the subscale intherate is An analysis of Eqs. [1], [2], and [3] shows that for a plate the rate is completely parabolic. The initial

Jan 1, 1970

By Norman J. Sather

LOCATION AND HISTORY The Bunker Hill Mine is situated on the south side of the Coeur d’Alene River in Shoshone County of Northern Idaho near the City of Kellogg. Kellogg, the largest in the Coeur d’Alene District cities, is at an elevation of 2,300 feet and has a population of approximately 7,000 people. It can be reached by air, railway or highway. The history of the Bunker Hill Mine dates back to August 26, 1885, when Noah S . Kellogg found the outcrop of the Bunker Hill ore body on the hillside above the present town of Wardner, Idaho, in Milo Gulch. A small concentrator was erected in 1886. Before the railroad came, the mine output was transported by mule teams to the head of navigation on Coeur d’Alene Lake. After ten years of production, an interest was purchased in the Tacoma Smelter at Tacoma, Washington, to which the entire output was shipped. In 1916 and 1917 a modern lead smelting plant and refinery was erected and in 1927 and 1928, a modern Electrolytic Zinc Reduction Plant was built and put into operation by the Sullivan Mining Company which was 50% owned and now totally owned by The Bunker Hill Company. GEOLOGY AND MINERALOGY The Bunker Hill ore bodies are found in gray and greenish gray quartzite and argillaceous quartzite of Precambrian age and are known as the Revett and St. Regis formations. Most of the ore bodies are found in the St. Regis formation.

Jan 1, 1970

By H. B. Bell, P. C. Lidster

A study has been made of the use of ThO2-Y2O3 solid electrolytes to determine activity of chromium in Fe-Cr and Ni-Cr alloys in the temperature range 1300° to 1700°K. This method has been shown to give results which agree with the best vapor pressure measurements. SEVERAL investigations1"5 have been made of chromium activities in Fe-Cr alloys. Most of these have been made by vapor pressure measurements using knudsen cell techniques while one has been made using gas equilibration with H2/H2O gas mixtures. In the present investigation electromotive force measurements have been made on this system using a thoria yttria solid electrolyte. This system was -chosen to establish the technique of measurement at low oxygen potentials, before extending it to Fe-Ni-Cr alloys. The cell used was Pt Cr • Cr2O3 ilThO2 • Y2O3 llalloy • Cr2O3 IPt Since the oxygen pressure of the chromium-chromic oxide mixture lay in the range 10"19 to 1027 atm in the temperature range investigated, thoria yttria electrolytes were used. It was soon found during the investigation that considerable care was required to prepare satisfactory electrolytes and a study was made to find the best method of preparing pellets of TI1O2-Y2O3 solid solution of as near theoretical density as possible. Various compositions in the range 2 to 15 mole pct Y2O3 were studied but the experimental measurements were made with electrolytes containing 4 to 5 pct Y2O3. The method of preparation finally adopted was to use thorium oxalate and yttria as raw materials. The thorium oxalate was decomposed at 900°C for 6 hr to give a reactive powder. This powder was then mixed with the appropriate amount of yttria and ground in an agate mortar for about 4 hr. The powder was moistened with absolute alcohol as a lubricant and pressed in a metal die at a pressure of 7 tons per sq in. The pellets were then heated at 1100°C for 24 hr followed by 24 hr at 1250°C. After this firing cycle the material was reground and repelleted and again fired at 1100° and 1250°C followed by heating for 7 days at 1600°C. It was found in later experiments that a further firing of 4 hr at 2000°C improved the density further and gave pellets of only 2 pct porosity. After firing, the pellets were polished on emery paper and finally with the 2 µ diamond paste. The polishing was followed by a final firing of 24 hr at 1500°C. Investigation showed that this final treatment minimized reaction between the electrolytes and chromium oxide. It was believed that this was because of a lowering of the surface energy of the electrolyte surface. Two types of investigation were carried out to check that the pellets were satisfactory oxygen ion elec-

Jan 1, 1970

By Freeman Bishop

Copper production has been under Government scrutiny for many years because it&apos;s known as a concentrated industry which in turn creates what many economists label administrative prices. Neither of these conditions is illegitimate, per se, the Federal Trade Commission and the Justice Department have said time and again. But Justice spoke up once more. This time over a Puerto Rican copper development planned by American Metal Climax, Inc., and the Kennecott Copper Corp. Bureaucratic Dichotomy Creates Confusion and Conflict In the Copper Industry Ian MacGregor, chairman and chief executive officer of Amax, said Justice in a recent communique questioned the propriety of the proposal of a joint copper venture in Puerto Rico. At the same approximate time, Dr. Hendrik S. Houthakker, chairman of the President&apos;s Commission on Copper, was urging copper producers to expand production to help hold down prices by making more copper available to all consumers. This, Mr. MacGregor said, is creating confusion and conflict, since the Administration from one source is chastising the industry for doing what another branch requests.

Jan 1, 1970

By J. Kittl, D. Arias

THE decomposition on cooling of the high-temperature ß bcc phases in copper- or silver-based binary systems usually takes place by a martensitic. massive, bainitic, or pearlitic reaction depending upon the particular conditions of each system. The AgAl system is one of these systems in which a massive or a martensitic transformation can occur upon cooling from the 3 phase field. Recently Hawbolt and Brown1 observed both massive and martensitic transformation products in a 22.7 at. pct A1 alloy. In the present work the massive and the martensitic transformations were investigated in a number of alloys for the composition range between 23.2 and 27.9 at. pct Al. The alloys were prepared using high-purity silver, 99.999 pct, supplied by ASARCO and aluminum, 99.999 pct, supplied by ALCOA. The metals were melted using a graphite or a sintered alumina crucible which was sealed in quartz tubes under an argon atmosphere. The alloys Were remelted to reduce segregation and homogenized in the 13 phase field for 24 hr. The weight of the alloys after homo-genization compared with the initial weight indicating the alloy composition to be within k0.1 pct of the in- tended composition. Chemical analysis of several samples confirmed the estimated alloy composition. All metallographic observations were performed on samples electropolished with ac current using a 10 pct solution of KCN and a stainless-steel electrode. The samples were cut into -1-mm-thick slices, polished, heat-treated in the ß phase field, and quenched in air, ice water, or iced brine. Some heat treatments consisted of a 2-min anneal carried out in air to allow maximum quenching speeds. Other samples were heat-treated in a vacuum of 10"4 torr and quenched using a helium blast in a quenching apparatus described elsewhere.&apos; In both cases, no appreciable losses of silver or aluminum were noted at the sample surface by sectioning and electropolishing. Table I summarizes the microstructure resulting from the various quenching treatments. The composition of the alloys investigated is also indicated on the equilibrium diagram in Fig. 1. The <, hcp phase, typical of a massive ß — cm, transformation, was observed in all alloys. A minimum temperature of 450°C was estimated for this transformation based on preliminary cooling experiments. the results being included in Fig. 1. In these

Jan 1, 1970

By O. N. Carlson, D. G. Alexander

THE hardness anisotropy of metals and alloys has been of increasing interest in recent years but silicon ferrite,1 niobium,2 and tungsten3,4 are the only bcc metals about which this type of information has been reported. This investigation was carried out on vanadium and chromium single crystals in an effort to determine to what degree the hardness variations observed in these metals are due to orientation effects and to compare their behavior with other bcc metals. In earlier work the authors had observed a small angular dependence in the Diamond Pyramid Hardness of single crystalline vanadium on the (100) plane but no anisotropic effects were noted on either the (110) or (111) planes. At the suggestion of R. G. wheeler5 it was decided to investigate this effect in greater detail using the more asymmetric Knoop indentor. The vanadium metal used in the study was prepared by the aluminothermic reduction of V2O5 followed by electron beam melting.6 The principal analyzed impurities were 230 ppm C, 230 ppm O, 65 ppm N, 90 pprn Al, Cr not detected, 50 ppm Fe, 60 ppm Ni, and 200 ppm Si. The chromium was an iodide-refined product obtained from the Chromalloy Corporation. Analysis of this material showed the following amounts of impurities present: 10 ppm C, 9 ppm O, 2 ppm N, 0.4 ppm H, 3 ppm Al, 2 ppm Ca, 2 ppm Cu, 20 ppm Fe, 1 ppm Mg, 0.3 ppm Mn, 1 ppm Mo, 3 ppm Ni, 10 ppm Si, and 1 ppm V. Single crystals of both metals about 1 cm in diam and 10 cm in length were grown by an arc-zone melt- ing technique.7 The chromium crystal was annealed at 1600°C for 6 hr in a purified argon atmosphere to remove any strains or inhomogeneities, but the vanadium was tested in the as-grown condition. The crystals were oriented by the Laue back-reflection method and then sectioned with a spark cutter into individual specimens with a (loo), (110), or (111) plane parallel to the crystal surface. They were mounted in Lucite and carefully ground to a flat surface. The vanadium specimens were then electropolished in a 6 pct perchloric acid-methanol mixture while the chromium specimens were mechanically polished on a Syntron vibratory polisher using an alumina abrasive. The orientation of each crystal was then rechecked by the back-reflection X-ray method. All of them were found to lie within 2 deg of the desired orientation with the exception of the (110)-Oriented chromium crystal which was within 4 deg. Microhardness impressions were taken at 10 deg intervals from the common (110) direction by rotating the crystal in the plane of the crystal surface. A Knoop indentor was used with a 400-g load on the vanadium crystals and an 800-g load on the chromium. The hardness values are averages of 6 impressions and standard deviations were calculated for each set of data. The values reported for the (111) plane of vanadium are based on from 10 to 15 measurements for each point. The microhardness results for vanadium and chromium are plotted as a function of the angular rotation of the long axis of a Knoop indentor from the (110)

Jan 1, 1970

By J. Douglas Gibson

In Canada, the economic climate for mining is still warm, but a noticeable chill set in last November when the Government published a White Paper on tax reform known as the Carter Report. Moreover, this chill could drop to a freeze injurious to the whole Canadian economy if two of the proposals in the Carter Report are adopted. The offending suggestions call for an end to (1) the depletion allowance and (2) the three-year tax holiday for new mines. Both of these tax incentives have played a major role in the postwar development of the Canadian economy and will, if undisturbed, play an even more important role in the future. The fact that they have worked and worked well is evident from the record. Fruits of an Industrial Beanstalk Excluding fuels, the value of Canadian mineral production was just under $3 billion in 1968-almost nine times as much as in 1946. With fuels included, the figure is $4.25 billion, or almost ten times as much as in 1946. Proportionately, this growth far exceeds that of Canada&apos;s manufacturers or of her economy as a whole. Table I traces the overall mineral production growth by principal products. Of particular interest here are petroleum, iron ore, natural gas, sulfur and potash, the combined production of which has grown from little or nil to a point where it now accounts for more than 40% of Canada&apos;s mineral output.

Jan 1, 1970

By George Steintveit

Det Norske Zinkicompani A/S was established in 1924, on the initiative of the Compagnie Royale Asturienne des Mines. Experimental electrothermic zinc production was carried out on industrial scale for a two-year period, but the problems of electrothermic smelting were not solved. A license for the electrolytic zinc production process was then obtained from the Anaconda Copper Mining Co. A plant for electrolytic zinc production was built, near the small fjord town of Odda in Hardanger, West Norway, The production was based on zinc ore from Spain, and cheap local hydro-electric power. The plant came into operation in 1929. Annual capacity, 36,000 tons. In 1964 a long-term agreement was concluded with Boliden AB by which Det Norske Zinkkompani is secured the raw materials basis for an expansion of the annual capacity to 100,000 tons of zinc, Since World War II, the company has been pursuing extensive research and development programs. As a result, various sections have been rebuilt: nev unloading and storage facilities, a 250 ton per day Fluid Bed Roaster with contact plant, new continuous leaching system, integrating the Jarosite Residue Process, new solution purification section - upgrading the solution quality for a 600 Amp/m2 current density Tank Room operation -, installation of induction furnaces for cathode melting with casting machines and automatic stacking of slabs. Simultaneously, instrumentation, and methods of automatic control have been developed and introduced, providing conditions for optimal plant operations.

Jan 1, 1970

By K. F. Clark

Some 30 years ago Stevenson (1940) underscored the fact that most of the world&apos;s molybdenite production came from the Cordillera that comprise the western part of North America, and that the northern extension of the Cordillera into British Columbia is not essentially dissimilar to the United States section. Therefore, in view of the successful development of molybdenite resources in the United States, he concluded that prospecting in the Canadian section f the Cordillera should be encouraged. However, as recently as seven years ago Schneider (1963) remarks that no large economic deposits have been brought into production in British Columbia, although one important property was being evaluated. World production f molybdenum ore was sporadic until 1900. Among the very early producing areas in North America were Arizona and New Mexico in the United States. World War I provided the stimulus that brought the Climax deposit into production, and in 1920 Questa, New Mexico followed, although the ore came from fissure vein deposits at that time. In the early part f this century high grade deposits in various parts f the world containing 5-20 percent MoS2 were exploited. In Canada most production during World War I came from Quebec and Ontario. With the build-up of world tension and the inception f hostilities in 1939, British demand was satisfied by United States producers (Schneider, 1963).

Jan 1, 1970

By C. B. Daellenbach

The influence of reduction roasting and thermal shock on the grindability of a refractory low-grade Michigan iron ore was examined in bench scale tests. The quantitative effects of the various treatments were evaluated at three sieve levels: 48, 100, and 400 mesh, using ball mill grindability and work index parameters as response indicators. Data from the testing program were analyzed statistically as a means of isolating the effects of cooling rate, roasting temperature, and ore chemical condition. All three variables were found to have an important influence on the grindability of the treated ore; ore chemical condition and roasting temperature had the most pronounced effects.

Jan 1, 1970

By J. H. C. Scrimgeour, T. Toong, R. E. Hamilton

"The principles involved in the use and application of mathematical models as an aid to the development of advanced process control computer systems are described briefly. This is followed by a brief survey of known models of this kind for the simulation of mining industry processes.The main part of the paper describes a dynamic model of the flotation process developed by Canadian General Electric. Using flotation rate constants for each species of mineral and gangue, the model provides a numerical solution of the differential equations describing cell behaviour. The cell mode] is used repeatedly as a subroutine in the •over-all-plant model. The features of the cell and plant models are described.Simulation runs from the plant model show stream .assays and other indications of plant behaviour printed typically in 1-to 10-minute steps for several hours of •Operation following typical disturbances such as changes in feed rate or reagent addition rate. The simulation can :Show expected behaviour for both uncontrolled and computer-controlled plants."

Jan 1, 1970

By Toshihisa Adachi, Shosei Serata, Shunsuke Sakurai

Many different methods of measuring the in-situ stress field have been developed in recent years. They are all based on the assumption of elasticity without allowing any viscoelastic deformation. By using the high resolution strain-measuring technique recently developed in the laboratory at Serata Geomechanics, many rocks were found to be viscoelastic. The viscoelasticity of rock media was found to be dependent upon the resolution of the strain measurement. The higher the resolution of the strain measurement, the greater number of rocks could be identified as viscoelastic. All rocks eventually exhibit viscoelastic deformation under high stresses relative to the strength of the material. Therefore, the conventional methods of elasticity become less reliable with increase of ground stress. In deep underground formations, even hard rocks become viscoelastic. At the same time, many ground formations near the surface are actually viscoelastic. A new method was developed in the laboratory to determine the in-situ stress field in viscoelastic rock media. Rocks in general exhibit a small amount of viscoelastic creep whenever mean stress and octahedral shearing stress are changed substantially from their initial states. Such changes take place around a borehole immediately following the drilling although they are short-lived. We developed a viscoelastic method of determining the in-situ stress field by relating the time-dependent behavior of the borehole with the tensor properties and stress field of the underground. In developing the viscoelastic relation, only isotropic and homogeneous

Jan 1, 1970

By R. W. Heckel, R. A. Tanzilli

ANALYTICAL results have previously been presented for the diffusion-controlled solution of a second phase in a finite medium for planar, cylindrical, and spherical geometries.&apos; These results were obtained by numerical methods using digital computer techniques and are applicable not only to the stage of the problem where the unstable phase shrinks to zero size, but also the subsequent stage where the concentration gradients in the matrix phase become negligible (essentially complete homogenization). It is anticipated that the results of such an analysis may be of use to those workers who are interested in the processes

Jan 1, 1970

Mine ore, reduced to minus 71/2 in. by primary crushers, is stockpiled. Size reduction of the reclaimed material by secondary and tertiary crushers is achieved in a closed circuit crushing and screening plant. Screen products of minus 30 mm plus 6 mm lump, and minus 6 mm fines are stockpiled by conveyor and stacker systems prior to rail despatch 10 port facilities at Dampier. Crusher settings, determined from experience, are closely maintained to obtain the desired lump/fines ratio. Chemical and sizing analyses from automatically taken samples are used to maintain product specifications. The beneficiation plant upgrades the fines product when this is necessary. The recorded wear life of individual plant components is the basis of a planned maintenance programme.

Jan 1, 1970

By A. S. Yue, A. E. Vidoz, F. W. Crossman

Tensile specimens were prepared from a single grain of an epitaxially grown Al-CuAl2 eutectic ingot. The eutectic lanzellae were oriented parallel and perpendicular to the tensile axis of the specimens. Since the composite was of the eutectic composition, the aluminum-rich matrix could dissolve up lo 5. 7 wt pct Cu in solid solution and, therefore, was amenable to strengthening by precipitation hardening. The tensile properties of the eutectic single crystals were determined at room temperature as functions of interlamel-lar spacing, platelet orientation, and thermornechanical trealment. The obserced variations in composite stress and modulus with respect to the level of&apos; composite strain are discussed in terms of premature fracture of CuAlz platelets, a distribution function for the strength of the lamellae, and unequal strains due to localized fracture of&apos; platelets. The discontinuous fiber composite model of Kelly and Tyson is modgied to account for a changing distribution of fiber lengths during composite loading. The tensile properties at elevated temperatures were determined for the direc-tionally solidified eutectic oriented with platelets parallel to the tensile axis. The observed properties are attributed to the onset of plasticity of the CuAL2 phase above 150°C. DURING the investigation of whisker- and fiber-reinforced metallic matrix composites in recent years, two major problem areas have developed: 1) The fabrication of the composite involves tedious handling techniques in order to obtain a unidirection-ally aligned and uniformly spaced set of whiskers in the metal matrix. 2) Due to weak interfacial bond strengths or because of the formation of additional embrittling phases at the metal-fiber interface during long-time exposure or fabrication at elevated temperatures, many composite systems have exhibited considerably lower strengths than those predicted by a law of mixtures analysis.&apos; These problems have been bypassed by the technique of growing whiskers and plates of high-strength materials in a ductile metal matrix by controlled unidirectional eutectic solidification.2 The tensile properties of directionally solidified A1-CuA12 eutectic are presented here. This alloy consists of a ductile aluminum matrix, containing up to 5.7 wt pct Cu in solid solution, which is amenable to precipitation hardening by heat treatment and a reinforcing high modulus CuAlz intermetallic phase. The two phases are present in the form of alternating platelets or lamellae. The microstructural stability of this unidirectionally solidified alloy at elevated temperatures has been studied extensively.3.4 and preliminary tensile and bend tests have been reported. 5-7In the present investigation the tensile properties of the A1-CuA1, eutectic have been studied as a function of several ther-momechanical variables: solidification rate. heat treatment. rolling at elevated temperatures. and lamellar orientation. It was felt that the uniformity of structure and excellent interfacial bonding would give tensile properties concomitant with the metal matrix composite theory of strengthening proposed by Kelly and coson. 8-9 The tensile properties that were obtained point to a wide distribution of strengths for the CuAlZ platelets, which leads to large deviations from the predicted mechanical behavior for this composite. EXPERIMENTAL PROCEDURE Epitaxial Growth of Eutectic Alloy. The A1-CuA1, eutectic alloy was prepared by an epitaxial growth process. Sections of a master alloy ingot (total impurity content <0.008 pct) were placed in an alundum boat, melted. and directionally solidified to obtain a multigrained plate 12 by 2 by 4 in. This plate was tapered at one end to mate with a seed crystal 1; in. long and 4 by $ in. square. Then the seed-plate combination was placed in an alundum boat which sat in a quartz tube passing through the center of a horizontal resistance wound tube furnace. A dried argon atmosphere was maintained. The temperature gradient in the furnace was such that the liquid-solid interface of the eutectic alloy was located near the end of the furnace and could be observed through the quartz tube. Single-crystal plates were formed by melting the material back to the midpoint of the seed crystal of the desired platelet orientation and then epitaxially growing the plate from the seed by withdrawing the alundum boat from the furnace at a constant rate. This technique was used to produce aluminum and CuA12 lamellae parallel and perpendicular to the transverse direction on the plate. Metallographic examination showed that both phases were continuous across the original liquid-solid interface. It was also possible to grow a plate from two seeds placed side by side: and, although the lamellae of one seed were oriented at 90 deg to those of the second seed, the interface between the two grains remained parallel to the growth direction along the entire ingot length. Maintenance of a straight intergranular boundary during the solidification process was possible as long as both seeds were oriented with their original growth direction parallel to the solidification direction of the plate. Eutectic plates were directionally solidified at rates of 0.2, 1.0. and 4.7 cm per hr and sectioned transversely to the solidification direction to determine the apparent inter lamellar spacing of the lamellae. Metallographic examination was also employed

Jan 1, 1970

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.&apos; These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,&apos; one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z&apos; alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970