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A rotating disc geometry was used to provide a uniformly accessible surface for a kinetic study of copper cementation with zinc in sulphate solution. For copper concentrations of the order of 10 p.p.m., a porous, adherent deposit is formed on the zinc surface and this has a significant influence on the reaction rate. When the specific mass of deposit is less than about O· 35 mg/cm2 the surface may be considered as smooth and the rate is described by simple convective counter diffusion of zinc and copper ions through a laminar diffusion boundary layer to the deposit-solution interface. In the presence of additional deposit, the diffusional mass transfer rate is increased by increased surface roughness.The rate under these conditions is first order, with the degree of enhancement independent of further increases in the specific deposit mass. The enhancement in rateis, however, directly related to the initial mass flux and the species involved in the reaction.Preliminary work showed the same mechanism to apply to cementation from chloride solution, solutions of high zinc concentration, and cementation of copper with iron..

Jan 1, 1970

By J. E. Udd, L. P. Geldart, B. B. Dhar

"Solutions for the stress distributions around simulated underground openings have been limited to calculations of boundary stresses for simple openings in which the boundaries may be expressed in mathematical terms. Studies involving circles, ellipses and ovaloids are re-ported in the literature.The stresses on the boundary of an opening and those at a distance from it in the medium are of concern to the engineer. The former may be related to the greatest concentrations of stresses encountered; the latter have a bearing on the identification of the ""zone of influence"" of the opening.Recent advances, in the form of a derivation for the stresses at a distance from an opening of elliptical shape, together with a solution derived previously for stresses in depth around ovaloidal openings, have been combined with computer programming techniques to provide complete solutions for a wide range of cases and variables. Some typical results which, it is hoped, may have some application to the design of underground openings are given herein."

Jan 1, 1970

By G. A. Chadwick, D. Jaffrey

The morpho1ogies and orientation relationships of the phases in the Sn-Zn and A1-A13Ni eutectic systems were examined by electron microscopy and X-ray diffraction techniques. In each alloy the "transition" from the lamellar to the fibrous morphology was found to be one of scale, not of type. The minor phase in both systems exhibited certain well developed facets which were not affected by changes in the ingot solidification rate. The crystallographic relationships displayed by the pairs of phases in both systems were also insensitive to the growth rate. In the Sn-Zn alloy, the unique relationship of: growth direction - II [1201 Sn - II [01101 Zn and ribbon interface plane 11 (101) Sn 11 (7012) Zn was determined. The Al-Al3Ni alloy phases did not possess any particular orientation relationship, though the Al3Ni phase invariably grew in the [010] direction and exhibited the same set of facet planes. These results are discussed in relation to current eutectic growth theories and explanations of the "lamellar to fibrous transition". THE lamellar to fibrous transition that occurs in many eutectic alloys has been the subject of considerable speculation and experimental study. In some alloys it can be induced solely by an increase in the solidification rate,'-3 whereas in others the transition supposedly occurs only if the lamellae are forced to grow out of the overall ingot growth direction.4-6 he cause of this latter type of transition has been attributed to deviations of the lamellae from their low energy habit planes;4'5'7 fibers are produced because the sustaining force for lamellar growth (a low energy boundary) is destroyed. Implicit in these explanations is the assumption that fibers are circular in cross-section and completely lacking in low energy inter-phase interfaces. The "natural" growth rate dependent transition has been studied less thoroughly although Tiller8 has attempted a theoretical explanation of it. Tiller's arguments are not completely satisfactory9 but his suggestion that the relative undercoolings of the solid/liquid interface for lamellar and fibrous morphologies are growth rate dependent cannot be totally discounted; it is possible, for instance, that the relative interfacial undercoolings could alter and produce the observed morphology change if the orientation relationships between the phases and the associated interphase bound- ary energies were sensitive to growth rate. Salkind et al." have reported finding a change in the orientation relationships in the A1-A13Ni system accompanying the lamellar to fibrous transition, but contradictory evidence has also been reported for this3'" and another system,12 so the position remains unclear. In an attempt to clarify matters a study was made of the "lamellar to fibrous" transition in the Sn-Zn and A1-A13Ni eutectic systems; the morphologies of these two selected systems are quite similar when viewed by optical microscopy. In the present research the morphologies and morphology changes were investigated by electron microscopy. The orientation relationships existing between the eutectic phases were also determined for both morphologies in both eutectic systems. EXPERIMENTAL PROCEDURE The materials and method of alloy preparation and ingot solidification for the Sn-Zn system have been reported previously.2 In this investigation nine horizontally grown ingots of the highest purity (99.9997 pct) were used. The temperature gradient in the melt was not intentionally varied and was approximately 10°C per cm. Seven growth rates between 1.3 cm per hr and 20 cm per hr were imposed. The A1-A13Ni alloys were prepared from "Spec. Pure" nickel and 99.995 pct aluminum by melting the components in an open alumina crucible and casting the melt into the cold graphite mold. Six ingots of the Al-Al3Ni alloy were unidirectionally solidified at growth rates from 1 cm per hr to 12 cm per hr under high purity argon. A typical ingot was 20 cm long, 1 cm wide, and 0.75 cm to 1.5 cm thick. Samples taken from the bars at positions 12 cm from the nucleation end were examined by conventional orthogonal-section metallo-graphic techniques. When required, samples were mounted for X-ray diffraction analysis using the Laue back-reflection technique with a finely focussed X-ray source. The surfaces of the A1-A13Ni specimens were prepared by mechanically polishing them down to the 1 µ diamond pad stage followed by an electropolish in 80/20 methanol/perchloric acid solution at 0°C and 20 to 30 v. The Sn-Zn specimens were repeatedly polished on an alumina pad and etched in hot dilute (2 pct) nitric acid until the diffraction spots were found to be sharp. Thin films of the alloys were prepared for observation in an electron microscope by spark machining thin discs (0.03 to 0.04 in. thick) from longitudinal and lateral sections of the bars and elec-trolytically thinning them via a jet polishing technique. For the A1-A13Ni eutectic alloy, an 80/20 mixture of ethanol/perchloric acid at 40 v and 20°C was found to be satisfactory. A solution of 70/20/10 methanol/perchloric acid/butylcellosolve at 25 v and 20°C was used on the Sn-Zn alloy. For the former alloy the jet nozzles (cathodes) and the disc clamps were of aluminum;

Jan 1, 1970

By J. C. Todd

The volume of air needed to move the combustion wave through each acre-foot of the reservoir is a very important quantity for engineering economic analyses. A new method, which involves backflowing the injection well, has been developed for determining the air requirement .for the forward combustion thermal pilot in the Delaware-Childers field. The method depends on measurement of the total volume of air injected and measurement of the pore volume in the zone swept out by the combustion front. The basic premise of the method is that the pore volume of the swept zone contains air, while the formation around this zone contains flue gas, oil and water. The pore volume of the swept zone is determined by blowing down the pilot section of the formation through the injection well after the pilot is shut down. Oxygen balance is used to differentiate between air from the swept zone and flue gas from the surrounding formation. Data indicate that air'is produced from the swept zone by relatively efficient miscible displacement by the flue gas. The pore volume occupied by the air in the swept zone is determined by simple PVT relationships. The average temperature of the swept zone is calculated by heat balance from the total amount of heat generated during the pilot and losses to the surrounding formation. The new method was applied successfully at the conclusion of the pilot in the Delaware-Childers field; the air required for the reservoir conditions involved was calculated to be 19.2 MMscf/acre-ft of reservoir swept. INTRODUCTION One of the most important pieces of information to be found from a forward combustion pilot is the air requirement; that is, the volume of air needed to move the combustion wave through each acre-foot of the reservoir. Compression costs per barrel of oil recovered, which are a direct function of the air requirement, are a large portion of the expenses incurred in the thermal recovery process. Thus, the profitability of thermal recovery depends largely on the air requirement, which is a measure of the amount of fuel deposited and burned in the thermal recovery process. Several attempts have been made to correlate crude oil properties with fuel deposition and, hence, air requirement.l*2 Other attempts have been made by our laboratory to find the air requirement by material balance, gravity survey, pressure transient analysis,3 magnetic survey and the poten-tiometric model. Better methods are needed to predict more accurately the economics of fieldwide application of the process. Another method of finding the air requirement consists of operating a pilot thermal project for several years. This is followed by an extensive coring program to define the volume swept by the combustion wave. The air requirement is found from the total injected air divided by the volume of the swept region found from the coring operation. This method is costly; an adequate coring program usually costs several hundred thousand dollars. A thermal pilot was operated in a watered-out portion of the Delaware-Childers field, Bartlesville sand, from Nov., 1960, until May 3, 1965. One of the primary purposes of this pilot operation was to determine the air requirement for economic calculations which determine the advisability of expanding the project to the entire 128,000 acre-ft field. Barnes4 has described the result of this pilot operation,, including calculation of the air requirement from limited coring data. The value obtained, as calculated, was 15.8 MMscf/acre-ft. One purpose of this report is to describe a new method of finding the air requirement from a thermal pilot operation. A second purpose is to describe the application of this method to the Delaware-Childers thermal pilot. THEORY AND DESCRIPTION OF THE METHOD The combustion zone in the forward combustion process is propagated from injection w producing

Jan 1, 1970

By A. J. Baer

"DEFINITION OF THE REGION AND ITS BOUNDARIESTHE EXPOSED PART OF THE GRENVILLE PROVINCE is the southeastern part of the Canadian Shield, characterized by crystalline rocks with K-Ar ages of about 1,000 million years. Its Canadian portion is bounded on the southwest by Georgian Bay •and by Paleozoic sediments south of a line passing through Orillia and Kingston, on the southeast by the St. Lawrence River valley and the north shore of the Gulf of the St. Lawrence, on the east by the coast of Labrador and on the northwest by the Grenville front, a linear tec-tonic feature that is a metamorphic transition zone and/or a fault. Rocks located to the southeast of the front have younger K-Ar radiom€tric ages than rocks located to the northwest of it.The region is formed of complexly deformed and highly metamorphosed crystalline rocks and in part differs from other areas of the Canadian Shield by the presence of large amounts of crystalline limestone and bodies of anorthosite."

Jan 1, 1970

By James S. Browning

The Bureau of Mines conducted laboratory and small-scale continuous tests of kyanite ore from Georgia to determine the technical feasibility of recovering commercial-grade kyanite concentrates by flotation. The research indicated that combinations of sulfuric acid and petroleum sulfonate may be used effectively for flotation of kyanite from quartzite-kyanite ore. Over 87 percent of the kyanite was recovered in a concentrate analyzing 55.8 percent A1203 and 5.3 percent acid-soluble Fe203. Subsequent treatment of the flotation concentrate by high-intensity wet magnetic separation reduced the acid-soluble Fe203 to 0.8 percent and increased the alumina content to 57.6 percent, with a recovery of 82.7 percent of the total alumina in the ore.

Jan 1, 1970

By Fathi Habashi

At the Duisburger Kupferhütte plant in Germany, pyrite cinder is collected from the sulfuric acid manufacturers in that country and processed to recover the nonferrous metals contained in the cinder, before charging it to the blast furnace for iron recovery. A typical analysis of the cinder is given in Table 9-1. The pyrite cinder is mixed with NaCl and treated continuously in a multiple hearth furnace. The evolved gases are scrubbed with water to form a weak acid which is used for the leaching process. Each batch requires about 2 days for leaching. The concentrated leaching solution obtained in the first 15 to 20 hr is sent for copper recovery, while that subsequently obtained, being poor ill metal content, is recycled. The residue, called purple ore, now a high-grade iron ore (61-63 % Fe); is sintered and delivered to the blast furnace.

Jan 1, 1970

A combined reflection seismic and magnetic survey off the south coast of New South Wales has revealed six distinct reflection horizons within the Lower Triassic-Upper Permian sequence, and has enabled the upper part of the lllawarra Coal Measures to be mapped in considerable detail. Large magnetic anomalies in the eastern half of the survey area appear to originate in the Gerringong Volcanic Sequence which forms the magnetic basement in the survey. Small residual anomalies in the western half of the area can be correlated with small scale faulting and folding in the upper part of the llawarra Coal Measures, as revealed by the seismic reflection survey.A synclinal axis striking at approximately 55° has been mapped near the western margin of the survey area, and areas of faulting and folding have been outlined by combined analysis of seismic and magnetic results.

Jan 1, 1970

By G. O. Prickett, P. Somasundaran

An experimental progmm based on statistical principles is used for optimizing a flotation operation for the separation of minerals. In this case, flotation of sylvite from sylvinite ore with amine and starch as the flotation reagents was studied to find the optimum reagent levels at various slime levels. The experiments were first done on a two-level three-factor design. Analysis of the results showed that the interactions between various factors were significant. Hence, a first-order linear model of the flotation response would not be accurate. The two-level three-factor design was expanded into a composite design in order to test the fit of a higher-order model. Data were treated to obtain an expression for flotation response as a function of the different variables, to predict the optimum reaaent levels at various slime levels, and also to determine the path of steepest ascent. Tests around the predicted optimum and along the path of the steepest ascent were done until a near-optimum region was obtained. Exploration of the nature of the response surface in that region established the actual location of the maximum response. The optimum amine level was found to be 0.20 lb of amine per ten of ore at all slime levels, while the optimum starch level varied as a function of the slime present. Computer access at the laboratory by means of a teletype terminal on a commercial time-sharing system enabled efficient and accurate treatment of experimental data. The efficiency of experimental investigations can be improved significantly by the use of experimental design and data analysis based on statistical principles. The common approach used in experimental research is to study a property of a system as a function of "one-variable-at-a-time". Several authors'-4 have pointed out the inadequacy and deceptiveness of this method. Results obtained for the effects of a variable on the measured response of the system using

Jan 1, 1970

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.' In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.' However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By R. H. Andrews, F. J. West

"Jones & Laughlin Mining Company, Ltd. operate the Adams mine at Kirkland Lake, Ontario, where they mine approximately 4,000,000 tons of extremely hard iron-formation and 3,500,000 tons of volcanic waste rock annually in order to produce 1,100,000 tons of iron pellets. This paper will discuss the maintenance of the four Model 1600 P & H shovels and the two 50-R drills used to obtain this production. The chief maintenance problems at the mine are due to the hard, abrasive ore and the cold winter weather."

Jan 1, 1970

By David N. French

In a recent paper, Miyoshi, Hara, and sugimotoL have shown that hardness increases and crack resistance decreases with polishing time in tungsten car-bide-cobalt alloys. They attribute the changes in hardness and crack resistance to cold working in these alloys. More recently Exner2 explains the decrease in crack resistance with the amount of material removed (polishing time) by suggesting that polishing removes a high compressive residual surface stress due to the initial grinding operation. He cites previous work on steel to show grinding can induce surface compressive stresses but offers no direct experimental measurements to support this in cemented tungsten carbides. In recent work we have observed changes in residual stress in the W C phase as measured by X-ray diffraction techniques with changes in polishing conditions.3 As a result of the work of Miyoshi et al.,L a brief study was undertaken to investigate the effects of polishing and grinding on the residual stress in the WC phase and have been reported.4 A single composition of tungsten carbide —10 wt pct Co was used. Two initial conditions were studied: an annealed condition with about -30,000 psi residual stress from the differences in thermal coefficients of expansion of WC and cobalt and, on the same specimen, a surface ground with a 150 grit diamond wheel. Stress was measured in the WC phase using X-ray diffractometry as a function of the amount of material removed by metallographic polishing with 6 diamond paste. The results are shown in Fig. 1. Two things are noted, 1) polishing with 6 p diamond paste has little effect on the annealed sample and 2) the magnitude of the grinding stress is markedly reduced as material is removed. By the time 0.1 mil is removed the surface has a metallographic polish satisfactory for light microscopy examination. Thus the surface, even though polished, can still retain most of the stress due to grinding. Since WC is itself slightly ductile, it seems reasonable that high compressive stresses can be generated in the surface by the plastic deformation accompanying grinding. Exner2 suggests, by analogy with steel, that as a result of grinding both WC and cobalt in the

Jan 1, 1970

By D. R. Jolley

"The selection of equipment for open-pit mining is an important decision which results in a considerable capital expenditure by the operator. The decision is complicated by the wide product range on the market. Certainly, equipment performance is an important criterion to consider in making the decision. Equally important, however, is the operating inter-relationship among the equipment. A poor balance increases production costs and waiting time as queues form at the bottlenecks. This inter-relationship is dependent on equipment performance, but it is also affected by management decisions (i.e. scheduling techniques).The purpose of this paper is to show how the computer is used to decide which equipment and operating decisions achieve the required production objectives at least cost. Actual mining of the pit is simulated over a period of time using different equipment and scheduling decisions. Production, waiting time and costs are evaluated for each alternative until the operator is satisfied that he has achieved the best result."

Jan 1, 1970

By A. L. Mular

In order to simulate a grinding circuit, it is necessary to obtain valid mathematical models of the grinding mills and classifiers in the circuit. Several models of grinding mills Ova been proposed 1,2,3 and models of cyclone classifiers are available 4,5. Those models developed by Lynch et. al. 3,5 have been tested in the plant, so that some degree of reliability can be placed on them. Because of this, it is reasonable to assume that the Lynch models will apply for a given circuit, and then to test this assumption. Empirical modifications are made as necessary for a given situation. Usually, valid simulation models can be modified slightly to provide control models6,7. The purpose of this paper is to describe the results of an approach taken by Mular8 to obtain the Lynch models of parallel cyclone classifiers being used in the A-circuit of the new Strathcona Mill***.This was one of the projects undertaken by the fourth year Metallurgical Engineering Class of 1969, Queen's University, Kingston, Ontario, Canada, as part of their process design course which cooperates closely with the Canadian metallurgical industry.

Jan 1, 1970

Plant based on the New Jersey refluxing process was installed at the Cockle Creek Works of Sulphide Corporation Pty. Ltd. to refine portion of the zinc output from the Imperial Smelting furnace.Refining of impure zinc is effected by distillation in two stages in vertical columns comprising a series of superimposed silicon carbide trays designed such that ascending zinc vapours and descending liquid metal are in intimate contact. In the first stage, portion of the zinc and its cadmium content are distilled from impure feed metal, condensed, and while still molten, fed to the second column in which zinc is boiled under controlled refluxing conditions to remove the cadmium content.The resultant zinc has a purity in excess of 99·995 per cent zinc.The availability of refined zinc has made possible the production of a number of zinc alloys for marketing in addition to the basic grades of zinc.

Jan 1, 1970

By E. G. Beinlich

The continuing search for faster, safer, and more economical methods of excavating underground openings has led the staff of the Mather mine of the Negaunee Mine Co. directly to mechanical boring of raises and drifts. The mine is located within the city limits of Negaunee and Ishperning in the eastern portion of the Marquette Iron Range in the Upper Peninsula of Michigan. It is owned jointly by McLouth Steel Corp., Bethlehem Steel Corp., Republic Steel Corp., and The Cleveland-Cliffs Iron Co., who also serves as the operating agent. A total of 2,400,000 tons of iron ore averaging over 60% Fe is mined annually by the block-caving method. This provides feed for the Pioneer pellet plant at Eagle Mills where 1,450,000 tons of pellets are produced yearly with the remaining tonnage being sold as coarse ore. Technical staff of Cleveland-Cliffs have long realized that improved methods of advancing raises and drifts were a necessity if underground mining of iron ore was to survive the transition period in the steel industry's requirements from direct-shipping ore to pelletized ores. For this reason, the Mather mine embarked upon an experimental raise-boring program with a prototype machine in 1961. Improvements since that time in equipment and practice have resulted in the acceptance of mechanical boring of raises as a standard development tool and a vital link in the fulfillment of an orderly development schedule. Advancement of large-diameter openings such as main-level drift headings by mechanical methods in the harder, more competent types of rock has developed more slowly in the mining industry due to the need for more compact and portable machinery and improved bit technology. Many of the obstacles have been overcome by the manufacturers, and in March 1967 it was decided to proceed with a program to bore approximately 4000 ft of 13-ft-diam drift in the Mather graywacke footwall rock.

Jan 1, 1970

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the 'a; and 'c,,' edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.' LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By S. Floreen, R. M. Pilliar, H. W. Hayden

The fracture behavior of a 50 pct Cu-50 pct Fe mi-croduplex alloy, laminated composites of copper and iron and an extruded 50-50 Cu-Fe elemental powder composite was studied. Very low ductile-brittle transition temperatures were achieved in all cases, but for different reasons. In the microduplex alloy both the initiation and also the propagation of cleavage fractures appeared retarded by the very small in-terphase distances. In the composites, crack propagation through the sumples was prevented in most cases by delamination fractures perpendicular to the advancing cracks. These delaminations occurred at different regions and by different mechanisms in the various composites. In the extruded powder composite, de-lamination appeared to take place along preexisting flaws. In the crack arrest geometry of the laminated plates, delamination took place by localized shear fractures within the copper near the Fe-Cu interfaces. In this case delamination was enhanced by thicker laminate layers, and by having the resistance to shear failure of the copper sufficiently low compared to the toughness of the iron. BRITTLE fracture in engineering materials has long been a problem, and many different ways of preventing it have been considered. One method that has been of growing interest lately is to prevent crack propagation by the introduction of mechanical discontinuities into the structure. These discontinuities may act in several ways. They may simply act as crack stoppers. They may introduce secondary fractures such as de-laminations that deflect the initial crack into new, less damaging directions. Alternatively, they may subdivide a fairly large bulk sample that would have been loaded in plane strain, for example, into a number of subunits that are individually loaded in plane stress and thus are more resistant to fracture. Other mechanisms, or combinations of mechanisms, are also feasible. A number of methods exist for introducing mechanical discontinuities into a structure. Composites by their nature have discontinuities in structure, and numerous studies have shown that fracture propagation in materials of this type can be radically changed by suitable control of the composite parameters. Of particular significance to the present work are recent investigations of layered composites made by joining high strength steel sheets by various means.'-4 These studies have shown that through proper control of the mechanical properties of the bonds joining the sheets it was possible to introduce delamination fractures that markedly improved the overall toughness of the composites and in some cases completely prevented through-the-thickness fractures. Another technique for introducing structural discontinuities is simply to use a two-phase alloy. It has been recognized for many years that a small amount of a second phase may improve toughness either by homogenizing plastic flow and thus preventing localized stress concentrations that nucleate fracture, or by interacting with an advancing crack. In most of these studies of two-phase materials, the decreases in ductile-brittle transition temperatures produced by the second phase were relatively small. More recently, work on two-phase stainless steels having a very fine grain microduplex structure has shown that the presence of on the order of 40 to 50 pct of a tougher second phase may lower the ductile-brittle transition temperature of the brittle phase by approximately 300°F. 5-7 In these alloys delaminations were seldom observed. The tougher second phase appeared to minimize the ease of both the initiation and the propagation of cleavage fractures. These results show that both the composite approach and the microduplex alloy approach are effective methods of preventing brittle fracture. Therefore, it was of interest to compare the fracture behavior of a microduplex alloy with composites made from the two-phases that were present in the alloy. To simplify this comparison the 50 pct Cu-50 pct Fe system was selected for study. At low temperatures the equilibrium tie line phases in this system are essentially pure ferrite and pure copper. A 50-50 alloy was cast and hot worked to produce a microduplex structure. Two types of composites were studied; laminated structures prepared by roll bonding iron and copper sheets of the tie line compositions, and an extruded powder composite made from high purity elemental powders. The fracture behavior of these materials was then compared. EXPERIMENTAL PROCEDURE Alloy Preparation. The 50-50 Fe-Cu alloy and the components for the roll bonded composites were prepared by vacuum induction melting 30-lb heats using electrolytic grades of iron and copper as charge materials. A carbon boil was used to deoxidize the melts. Small additions of copper and iron were made to the iron and copper heats, respectively, to approximate

Jan 1, 1970

By Morris E. Fine, Richard A. Kloske

The stress-strain beha1,ior in tension of Au-Ag alloy single crystals containing nominally 1,3, 5, 95, 97, and 9.9 at. pct Ag was studied uS strain role and lektlperalure down lo 4.2K. A slrain aging yield hob lc,rrs observed on aging under stress in the temperature range 30° lo 75°C. The species diffusing to the dislocation is thought to be a divacancy-solute complex wilh /he. solute then pinning the dislocation by short-Range ovdering and possibly Suzuki locking. At room tempevullcve the critical reso1ved shear stress .follo~c.s an empirical equation of the form tc = A +Bc' where A and B are 90 and 420 ,g per sy mm tor gold base alloys and 60 and 510 g p~r sq )11ttz .tor si1ver base alloys. This strengthening was attributed to a long-range size ejtect. The alloy slrenglliening at i.2'K is greafer than at room temperature. The additional atrloutzf was altribuled lo a uwak skovl-range i?~levacIion between the solute and dislocallon cove. The activation energy .tor deformation a/ 4.Z0h7 decreases on alloying. 11 increases irr other fee systetns. hi the 5 at. pcl Air-Ag- alloy in pmvlicular there is very extensive easy glide and lavge overshooting- of the synmetry line at 4.Z°K. There is also u sharp decrease in the vale of. strain hardenitlg near the widdle of stage II with the new rate bezng abold the sarne as tlzal In easy glide. This uws attributed to a sudden reduction of activity on the pvitrrarg sgstertr. In Au-Ag alloys the critical resolved shear stress Tc. at room temperature is essentially a parabolic function of atomic concentration:' the 50 at. pct Ag-50 at. pct Au alloy is about 10 times stronger than the pure metals. This strengthening occurs in spite of the similarity in valence and atomic size. Solid-solution strengthening in fcc metals is characteristically greater at low temperatures than at room temperature. In Ag-10 at. pct Au and Au-10 at. pet Ag; r, (20.4K)/Tc (300°K) is 2.3 and 2.5. respectively.- compared to 1.2 in pure silver.3 Suzuki' and Flinn5 explained the alloy strengthening at room temperature as a combination of Suzuki locking and short-range order hardening. The agreement between the computed and measured strengthening was very good: however, in Ag base-A1 alloys Hendrickson and Fine6 concluded that Suzuki locking resulted mainly in a yield drop effect. Recent reviews of the solid-solution strengthening in fcc metals by Fleischer2 and Haasen8, 9attributed the strengthening at room tenl-perature to the combined effect of atom nlisfit and change in shear modulus 011 the long-range stress field surrounding a dislocation. The parameter used by Fleischer was The shear tnoduli of Ag-0 to 6 at. pct Au alloys were measured by Pur-wins. Labusch. and Haasen.In While addition of 4 at. pct Au caused an appreciable increase in the C,, elastic constant. there was a decrease on increasing the solute to 6 at. pct Au: C,, and C :: were not measured in the 6 at. pct alloy. The greater solution hardening at low temperatures implies the presence of short-range interactions between the solute atoms and dislocations These include size and electronegativity effects. Whether the extra alloy strengthening at low temperatures is due to locking or friction hardening is still a controversy."".' In the present research the stress-strain behavior of Au-Ag single crystals containing 1 to 5 at. pct Ag and 1 to 5 at. pct Au was measured vs strain rate and temperature down to 4.2' K. Particular attention was paid to yield drop effects. These have not been previously reported. PROCEDURES The alloys were supplied by the Engelhard Industries. Inc.. as strips 0.050 by 0.250 by 12 in. The compositions are given in Table I. Single crystals were grown under static vacuum using a traveling molten zone technique. Crucibles shaped to the size of the strips were made of high-purity graphite prebaked for 24 hr at 1100°C in vacuum. The crucible and its charge were placed in

Jan 1, 1970

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3'4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970