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By W. A. McKinney

In conventional dump leaching of porphyry mine strip wastes, many years are required to extract up to 20 percent of the copper from the contained sulfide minerals. Furthermore, none of the molybdenum, gold, or silver in the strip wastes is recovered by current leaching practices. Because mineralization occurs predominately along fracture planes, breaking of the rock during mining operations liberates and concentrates some of the metal values in the fines. Research shows that upgraded fines can be screened from mine wastes and froth floated for early recovery of copper, molybdenum, gold, and silver. For example, screening a dump sample assaying 0.35 percent copper as chalcopyrite removed about 20 percent of the copper as minus 1/4-inch material that analyzed 0.6 percent copper. About 35 percent of the molybdenum and 20 percent of the gold and silver also reported in the fines. Crushing the mine dump sample to minus 3 inch before screening increased the distribution of copper and molybdenum in the minus 1/4-inch screen fraction to 28 and 50 percent, respectively. Similar results were obtained by screening fines from two other large samples of mine waste dump materials. Flotation studies established that the enriched minus 1/4-inch fines from the three dump samples could be effectively concentrated. Comparative testing revealed that the combination of froth flotation of fines and acid-ferric sulfate leaching of the coarser fraction enabled doubling the recovery of copper over direct leaching of the samples. In addition, significant amounts of molybdenum, gold, arid silver were recovered by flotation.

Jan 1, 1970

By Carl L. Bieniewski

U.S. molybdenum production increased fivefold from 18.2 million pounds in 1946 to 90.5 million pounds in 1966, and constituted 87.3 percent of the total free world supply in the 1946-66 period. Mining development in other free world countries in the next few years may reduce the magnitude of the U.S. position, although similar development planned for the United States may counteract some of the relative gains by those countries. In 1966 two-thirds of the reported molybdenum consumption in the United States by end uses was as an alloying element in steel. Molybdenum also has important use as an alloying element in iron and high-temperature alloys. Consumption of molybdenum metal for making fabricated parts has increased in the past few years, especially in the space and nuclear industries. Molybdenum compounds are used mainly for making pigment, catalysts, and lubricants. Based on producer reports of shipments of primary products to domestic customers, U.S. consumption of molybdenum increased from 16.5 million pounds of molybdenum in 1946 to 65.6 million pounds in 1966. U.S. molybdenum reserves are now estimated to be 5.9 billion pounds of recoverable molybdenum, an increase of 2.1 billion pounds above previous estimates. Molybdenum ores account for 71.4 percent of the reserves, copper ores for 22.3 percent and copper-molybdenum, tungsten, and uranium ores for 6.3 percent. Several methods for predicting future demand are illustrated and estimates of demand using these methods were made for 1975. Based on present capacities and announced company plans for future developments, estimates of annual production were made for 1967 through 1975 for the United States, Canada. Chile, Peru, and the free world. These data indicate that molybdenum production in 1975 for the free world is expected to be 246 million pounds with the United States producing 68.2 percent and Canada, Chile, and Peru 30.3 percent.

Jan 1, 1970

By Alfred E. Schwaneke

A new high-temperature soft soldering system has been developed by the Bureau of Mines for use on copper, copper alloys, and low-carbon steel; the method is applicable to automobile radiators and home appliances. The system uses a unique sacrificial metal coating method to promote spontaneous wetting and spreading of zinc and zinc alloy solder: on metallic substrates. The 10-5 to 10-6 cm thick, electroplated or sputtered, sacrificial nickel coating is absorbed by the molten filler alloy during soldering and produces a direct solder-substrate metallic bond. Preliminary measurements on butt joints with copper members give tensile strengths up to 22,000 psi at room temperature using 95 Zn-5 Al alloy as solder. Spontaneous wetting, spreading, and capillary penetration are extremely rapid and produce joints as easily as 50-50 tin-lead solders. Recrystallization or annealing of the wrought copper joint members is negligible at the soldering temperatures of 450° to 490° C and lower. A list of fluxes and solder alloys is included in the report.

Jan 1, 1970

By J. Howard Boyce

INTRODUCTION The Tsumeb Mine is situated in the northern part of South West Africa, approximately 335 air miles north-east of the port of Walvis Bay on the Atlantic Coast, and 240 air miles north of Windhoek, the capital of South west Africa. The mine came into operation in the early 1900's and has operated continuously since then except during the two world warm and the depression years of the thirties, Tsumeb Corporation purchased the property in 1947, installed a new plat, and ham built a modern tom. In addition to the concentrator which began operations in 1948, a copper smelter was started in 1962 and a lead smelter in 1963, Tonnage of ore treated in the concentrator has varied through the years, reaching a maximum of 70,000 tons per month with a current mined tonnage of approximately 50,000 tons per month. Copper concentrates, lead concentrates and zinc concentrates are produced, and for a number of years the production of a germanium enriched concentrate was an important feature of the operation, Both copper and lead concentrates are smelted in Tsumeb, while the zinc concentrates are shipped overseas. Ore change, and the installation of the smelters in Tsumeb have necessitated modifications in the concentrator operation. This paper will describe current plant practice in some detail and will touch briefly on the techniques used from 1954 to

Jan 1, 1970

By M. Duclos, A. Sawatzky

A simple model has been developed which describes the steady-state solute distribution in Ti-H type systems above the eutectoid temperature in the presence of a temperature gradient. The solute distribution is dependent on the shape of the phase boundaries. An interesting result, and one that is not observed at steady state in thermal diffusion below the eutectoid temperature, is the existence of a two-phase region. The heat of transport for hydrogen in a titanium, Q*a, over the temperature range 275" to 650.C is determined to be 4500 * 230 cal per mole. The heat of transport for hydrogen in B titanium, QB* over the temperature range 320" to 590.C is found to be 630 ± 200 cal per mole. It is also shown that thermal diffusion provides a method by which phase bounduries above the eutectoid may be determined in Ti-H type systems. IN modern technology materials are being used at constantly increasing temperatures under greater temperature gradients. Thus atomic migration in metal alloys due to a temperature gradient (thermal diffusion) may in some cases occur to an observable extent. The thermal diffusion of hydrogen in zirconium has in recent years received considerable attention1-' because of the use of zirconium alloys in nuclear power reactors. The thermal diffusion kinetics below the eutectoid (547°C) are fairly well understood. At steady state the solid solution, a, and hydride, 6, phases are completely separated with the hydride precipitating at the lower temperatures. No experimental work has been carried out in the a + B region although Droege4 suggested that a complete separation of the two phases, as observed at temperatures below the eutectoid, might not always occur. In the present investigation a simple model has been used to determine the steady-state solute distribution under a temperature gradient in Zr-H type systems heated above the eutectoid temperature. The solute distribution is shown to be dependent on the shape of the phase boundaries in the constitutional diagrams and several typical cases are discussed. The model has been applied to Ti-H. This system was chosen in preference to Zr-H because of its much lower eutectoid temperature (-300°C as compared with 547.C), thereby reducing experimental errors due to oxidation and hydriding. The heats of transport for hydrogen in the a and B phases of titanium also have been determined since they were required to compare the proposed thermal diffusion model with experiment. THEORY In the presence of a temperature gradient the atomic flux in a single-phase region of a two-com-ponent system of which the atoms of only one component are diffusing is given by:' J = - U\dx + RT3 dx) which can be written as: j-D(dn/dt +Q*n/RT2)dt/dx [11 J - -D\dT + RT2)dx [1] where D = diffusion coefficient, n = solute concentration, T = absolute temperature, R = gas constant, dT/dx = temperature gradient, and Q* = heat of transport. At steady state (J = 0) Eq. [I] leads to the solute distribution: n = noexp Q*/RT where no = a constant depending on total solute content. The heat of transport Q* can be experimentally determined from the steady-state distribution. In the present paper we shall determine the solute distribution in systems having the constitutional diagram exemplified by Ti-H shown in Fig. l.' As shown, N,(T) and NB(T) are the equilibrium solute concentrations in the a and 0 phases at temperature T. Lines AA' and CC' define the region of interest to us. The following assumptions are made: 1) Steady-state conditions prevail. 2) In a single-phase region all points on an isotherm have the same thermodynamic potential so that the composition over an isotherm is uniform. If a two-phase region exists, thermodynamic equilibrium is found only at phase interfaces. However, we assume the component of the concentration gradient along an isotherm to be small so that the composition in each phase is approximately the same as at the interface and is given by the constitutional diagram, Fig. 1. 3) There is appreciable diffusion of only one component. 4) We shall consider only the case where Qa*, QB*, and Qg*, the heats of transport for solute diffusion in the a, B, and 6 phases, respectively, are positive. This has been observed for the thermal diffusion of hydrogen in zirconium3 and titanium.10 We will show that the steady-state solute distribution above the eutectoid is primarily determined by the heats of transport and the temperature dependence of Na(T) and Np(T). It may be quite different from the steady-state distribution below the eutectoid. For example, we will see that, under certain conditions,

Jan 1, 1970

By Thomas J. O’Neil

From the time of its emergence as an independent state until the late 1950's, the Republic of Ireland suffered from chronic unemployment, the lowest living standard in Northern Europe, and-most serious of all-an aggravated emigration problem which drained off most of its talented young people. In 1958, however, there was a drastic legislative reaction to these problems, and this in turn ignited the current mining boom in Ireland. Paving the Way to Prosperity In order to reverse the tide of emigration, the Irish government now realized, challenging domestic employment opportunities had to be increased and living standards had to be raised. It was also apparent that future industrial and economic growth in Ireland had to be based on producing goods for export. The home market could not sustain large-scale expansion, and consequently Ireland's chronic balance-of-payments deficit could best be minimized by producing export goods. These considerations, together with the limited amount of accumulated wealth in Ireland, combined to set the objectives of the country's First Program for Economic Expansion in 1958. The general objectives of this program were (1) to stimulate all segments of the economy, (2) to develop foreign trade and (3) to attract foreign capital.

Jan 1, 1970

By J. Vance Batty

The Permian Red Bed copper deposits of the South Central States are a potentially important resource. Only the higher grade, near-surface ores are now exploited because conventional froth flotation does not recover oxidized copper minerals which comprise 10 to 15 percent or more of the copper content of typical ore. Laboratory-scale beneficiation studies were initiated to devise a method capable of recovering both sulfide and oxidized copper mineral. Testing established that the high clay and gypsum content of typical ore prevented effective flotation of the oxide mineral using sulfidizing, fatty-acid, or oil emulsion techniques. A modified leach-precipitation-flotation (L-P-F) procedure recovered over 90 percent of the copper, compared to a recovery of 77 percent obtained by conventional sulfide flotation. The higher costs of the L-P-F method would reduce the increased revenue from higher copper recovery. An increase in copper price and/or an increase in oxide copper content of the ore would make the L-P-F process comparatively more attractive.

Jan 1, 1970

By T. Olrog

Dissemination of technical data on developments in rock-blasting techniques in Sweden initially takes place as personal contacts and contacts between companies. In addition to these informal contacts, contacts occur in Sweden in a somewhat more organized form. There exists an informal working group--the Rock Blasting Committee--which consists of a number of personal representatives from various companies that perform rock blasting on a large scale and from firms manufacturing the equipment that is used. This means that people from both mining and construction companies get together, plus the manufacturers of explosives, drill steel, drilling machines, and loading equipment. This working group has, so far, succeeded very well in ignoring the purely commercial interests of the companies concerned. Cooperation in this form was started in the 1940's when the tungsten-carbide drill steel was invented-the group originally concentrated entirely on the development of that product. Their activities have been broadened since that time and now a meeting is held every year, at which practical experiences are reported. Only in the past five years have subjects relating to blasting procedures to avoid rock damage been treated at such meetings. This, of course, does not mean that such techniques had been neglected previously. It does, however, reflect the fact that practice in this field is still under development. Why do we try to be careful about the rock surfaces? Obviously, it is a question of economic evaluation. An even rock surface provides, in certain cases, the conditions for more favorable maintainance costs later on, greater strength, and a diminished risk of slides. The economic connections in this field, however, are neither simple or clear. A well-controlled blasted rock surface limits the need for concrete when you later build the concrete constructions. In this respect, the connections are all the more clear. In certain situations, such as tunnels for hydroeletric power plants, a good rock surface that is not lined is hydraulically more favorable than a more coarsely blasted surface. This permits a gain in the height of fall, but the

Jan 1, 1970

By C. F. Swab

A relatively innocuous halocarbon was investigated as a substitute for the highly toxic carbon tetrachloride in the approval testing of chemical cartridges. The vapor effluent of 1,1,2-trichloro-1,2,2-trifluoroethane from chemical cartridges is continuously monitored by a nondispersive infrared analyzer. Breakthrough times for the cartridges, using the halocarbon, can be equated to those of carbon tetrachloride, if multiplied by the factor, 1.49.

Jan 1, 1970

By E. B. Wilson

"Although the Operations Research technique of Reliability Theory has been applied with marked success in many fields, including the Apollo spaceship programs, the concept of reliability has not been generally adopted in mining and other heavy industries. Of course, reliability, or the probability that a system will be able to operate without a failure for a given interval of time, does not require the same emphasis in mining as in the aerospace industries. Nevertheless, certain aspects of Reliability Theory can be followed advantageously. For example, reliability calculations can determine the best time to overhaul and whether to retain stand-by units.The usefulness of the pseudo-operations research technique known as Replacement Theory is more readily re-cognized by the maintenance engineers in mining and other heavy industries. One of the least complex models enables the optimum Lifetime of an asset to be determined."

Jan 1, 1970

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

Jan 1, 1970

By Sub-Committee of the Committee on Research

"THE FOLLOWING REPORT was compiled by a sub-committee of The Metallurgical Society of CIM, Committee for Research, and represents a viewpoint of the steel industry in Canada. The objective was to define those areas in which the industry considers that external sources of Research and Development are a necessary function in supporting the in-house R & D conducted by the industry.On future occasions, the viewpoints of other metallurgical industries, such as those of nickel, copper and aluminum, will be presented. The report is divided into several sections: 1.-R & D Spending by the Steel Industry (a) Memberships in Recognized Steel Research Centres (b) Memberships in Recognized Industry Associations (c) Sponsored Research at Recognized Centres (d) Sponsored Research at Universities(e) Sporadic Research 2.-Areas for Research and Development(a) Instrumentation (b) Environment Control (c) Refractories (d) Sponsored Research at Universities(e) Electric Furnaces (f) Continuous Casting"

Jan 1, 1970

By Cuppam Dasarathy

THE object of this note is to report briefly certain results of investigations on the Fe-In phase diagram. BISRA-high purity H-iron and 99.9 pct pure indium were used to prepare the alloys. The experimental techniques consisted of thermal analysis, optical metallography, and X-ray diffraction. A phase diagram based on the present results as well as those reported earlier by the author' is shown in Fig. 1. It is seen that the liquidus points fall on a smooth line which meets the monotectic isotherm at 1470°C. The liquidus extends up to 3.4 at. pct In. The phase boundary separating the two liquidus L1 and L2 is shown dotted. The experimental solidus meets the monotectic isotherm at -0.9 at. pct In. The 6/6 + L2 boundary drops steeply to the 6 + La/y + L2 boundary at -1350°C. In this region, it is impossible to detect satisfactory thermal arrests because of the steep phase boundary. The present diagram shows that indium lowers the temperature of the d/y transforma-tion and raises the temperature of the y/a transfor-mation. The y +d region is found to be very narrow. Indium gives rise to a restricted y field when alloyed with iron. The width of this field is between 0.4 and 0.5 at. pct In. Details of the alloys containing 40 and 50 at. pct In have already been reported by the author' and the transformation temperatures of these alloys are included in Fig. 1. It appeared from optical metallography and X-ray diffraction that the room temperature solubility of indium in a iron is less than 0.28 at. pct since alloys of 0.28 at. pct In and above, slow cooled to room temperature, contained dark etching second phase particles situated both in the matrix and grain boundaries of the a-grains, see Figs. 2 and 3. These particles were identified to be unalloyed indium by X-ray diffraction. The lattice parameter of the a phase reached a maximum of 2.8672A at the indium level of -0.28 at. pct. The present diagram, Fig. 1, is in substantial agreement with that of Stadelmaier and Fiedler' except for certain differences in detail. For example, they found the monotectic composition and temperature to be 7.0 at. pct In and 1443oC, respectively, while the present work indicates them to be 3.4 at. pct In and 1470°C. The 6 + L2/y + L2 transformation is indicated in the present work to occur at -1350°C, whereas Stadelmaier and Fiedler find this to occur at -1320°C. They also claim that the width of the y field is 0.2 at. pct In while the present work shows the width to be between 0.4 and 0.5 at. pct In. 1) Indium, when alloyed with iron, gives rise to a restricted y field, the width being >0.5 at. pct In.

Jan 1, 1970

By Frank C. Andreuzzi

The Division of Environmental Activities, U.S. Bureau of Mines, conducted a solid waste demonstration project on a burning coal refuse bank. The primary objective of this project was to develop and evaluate an efficient method of extinguishing burning coal refuse and moving it. A series of tests were performed using water monitors and related apparatus to quench the burning material and, at the same time, using earth-moving equipment to transport, spread, and compact the extinguished material. The method found to be most effective consisted of water-quenching the surface material to a workable depth, ripping, and removing the quenched material with a bulldozer and tractor-scraper. The total cost was estimated to be $0.44 per cubic yard.

Jan 1, 1970

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By M. J. Richards, A. Szirmae, G. R. Speich

The formation of austenite from ferrite, ferrite plus retastable carbide, spheroidite, and pearlite has been studied in a series of irons, Fe-C alloys, and plain-carbon steels using fast heating techniques. In the absence of carbide, austenite nucleates at ferrite/ferrite grain boundaries; nucleation is followed by the rapid growth characteristic of a massive transfornation. The trarnsformation occurs at 950°C at heating rates of 106º C per sec and cannot be suppressed. Metastable carbide dissolves before austenite forms and does not influence the transformation kinetics. For spheroidite structures, austenite nucleates preferentially at the jinction between carbides and ferrite grain boundaries. Growth from these centers proceeds until the carbide is completely enveloped; subsequent growth occurs by carbon diffusion through the austenite envelope. For pearlite structures, austenite nucleates preferentially at pearlite colony intersections. Carbide la)?zellae dissolve at the advancing austenite interface but complete solution of carbide does not occur; the residtial carbide is eventually dissolvled or spheroid-ized depending on the carbon cuntent. The magnitude and temperature dependence of the austenite growth rate into Fe-C pearlite when incomplete carbide dissolution is assumed are satisfactorily explained by an approximate colume diffusion model. The impurities present in plain-carbon steel reduce the growth rate of austenite in comparison to that jound in an Fe-C alloy. The formation of austenite has been studied in much less detail than the decomposition of austenite. This is primarily a result of the importance of harden-ability in determining the mechanical properties of steel. Recently, more interest in the kinetics of austenite formation has resulted from the discovery by Grange1 that rapid heating techniques strengthen steel by refining the austenite grain size. Although the strengthening effect is not large, it is accompanied by no loss in ductility. In addition, interest continues in rapid heat treatment of low-carbon steel sheet for tin plate applications.2,3 Among the few systematic studies of austenite formation are the early work of Roberts and Mehl4 on formation of austenite from pearlite and recent work of Molinder5 and of Judd and paxton6 on formation of austenite from spheroidite. Also, Boedtker and Duwez7 and Haworth and paar8 have recently studied the formation of austenite from ferrite in relatively pure iron, Kidin et al.9,10 have studied the formation of austenite in 8 pct Cr steels, and Paxton has recently discussed various aspects of austenite formation in steels." The present work was undertaken to determine the kinetics of austenite formation for a variety of starting structures including ferrite, ferrite plus metastable carbide, ferrite plus spheroidal cementite, and ferrite plus pearlitic cementite. Emphasis was placed on determining the active sites for austenite nucleation, determining the temperature and time range of austenite formation, and in the case of pearlite a careful study of the growth rate of austenite was made in the absence and presence of impurities. By using a variety of heating techniques including laser-pulse heating, it has been possible to study austenite formation in an isothermal fashion over a wide range of temperatures. EXPERIMENTAL PROCEDURE The alloys studied in the present work are a zone-refined iron with 4 pprn C, an Fe-C alloy with 130 pprn C, 2 Fe-C alloys with 0.77 and 0.96 wt pct C, and a plain carbon steel with 0.96 wt pct C. The zone-refined iron and Fe-C alloys contained 60 pprn and 200 pprn total substitutional impurities, respectively. The plain carbon steel contained 2400 pprn Si, 2000 pprn Mn, and 900 pprn Cr. Various heat treatments were given to these alloys to produce different starting structures of equiaxed ferrite, ferrite plus metastable carbide, fine pearlite, and spheroidite. These heat treatments are given in Table I. A wide range of heating rates were employed in this work because many of the reactions occur so quickly at temperatures in the austenite range that they are completed during the initial heating cycle unless very fast heating rates are used. Essentially the same heating techniques employed by Speich et a1.12 and Speich and Fisher13 were used in this work. For time intervals of 2 sec to 20 hr, simple hand immersion of 0.010-in. thick specimens in a Pb-Bi bath was employed. These specimens were quenched in a 10 pct NaC1, 2 pct NaOH aqueous bath. For time intervals of 100 m-sec to 2 sec, an automatic dunking and quenching device was employed with 0.002-in. thick specimens. Again, liquid Pb-Bi baths were used for a heating medium but now helium gas quenching was employed. For time intervals of 2 to 100 m-sec a laser heating device was employed with 0.002-in. thick specimens; a helium plus fine water-droplet spray was now used for quenching. Additional information on heating times shorter than 2 m-sec was obtained by study of the zones around the centrally heated laser spot. Here diffusion of heat from the centrally heated zone raises the temperature of the specimen locally to all temperatures between ambient and the peak temperature, but for times of the order of microseconds. All the heat-treated specimens were examined by

Jan 1, 1970

By B. J. Dalton

Several relationships between coexisting phases for analytical binary solutions near the critical point are given. These relationships were developed from a consideration of a (G u, P) surface at constant temperature and a (G u, T) surface at constant pressure, where G is the molal Gibbs free energy, u is the concentration of component 1 expressed as a mole fraction, G is the pressure, and T is the temperature. These formulas should facilitate the calculation of some of the quantities useful in making thermodynamic consistency checks on phase equilibria data about the critical point.

Jan 1, 1970

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970