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By E. C. Houston

The phosphate ores mined in middle Tennessee typically consist of granular rock phosphate particles disseminated in a clayey matrix. In the TVA plant near Columbia, Tenn., the phosphate ore is mined, made into a slurry with the addition of a small amount of sodium hydroxide as dispersant, and treated in a hydroseparator to remove minus 10 micron material. The hydro-separator underflow, comprising a rough concentrate, is transported by pipeline to the plant; the hydro-separator overflow, comprising a tailing, is flocculated by addition of calcium sulphate and is discharged to settling ponds at a rate of about 1400 gpm. Sedimentation in the ponds produces a clarified effluent, which may be recycled for use as process water or discharged to surface drainage. This method of tailing treatment is not entirely satisfactory since poor sedimentation characteristics of the tailing result in poor ultimate utilization of pond storage volume.

Jan 1, 1949

By W. L. Saunders

THE world's greatest producing area is, geographically, in the midland region of North America about the Great Lakes. This area, with but one- third of the nation's population, produces, with the exception of tobacco and cotton, three-quarters of the principal staples. It provides the surplus or export grain, meats, dairy products, steel and leading minerals. The social and political condition of a nation is determined by its industrial efficiency, and the share of the commerce of the world obtained by a nation is fixed more by the economy of its transportation than by any other factor. It is an economic maxim that: The total cost is the cost of production plus transportation cost. The cost of carrying 1000 tons by water or 100 tons by rail is equal, over the same distance

Jan 1, 1921

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

ST. LOUIS SECTION EUGENE MCAULIFFE, Chairman, J. N. HOUSER, Vice-chairman, VICTOR RAKOWSKY, Vice-chairman., H. G. WASHBURN, Vice-Chairman, W. E. MCCOURT, Sec'y-Treas., Washington University, St. Louis, Mo. H. A. BUEHLER, G. H. COx, L. C. GLENN, E. A. HOLBROOK, W. E. NEWNAM. The eighth meeting of the St. Louis Section was held at the Mercantile Club on Apr. 15, 1918. ,, The meeting was preceded by a dinner, at which 51 members and guests were present, and at which T. T. Brewster presided. Bradley Stoughton, Secretary of the Institute, and Major J. R. Fordyce were the guests of the Section. A number' of the Joplin members were obliged to leave before the close of the dinner, in order to make train connections. The Vice, chairman, therefore, called on Victor Rakowsky, who brought a message of greeting from the Southwest district. At the close of the dinner, the Vice-chairman, T. T. Brewster, introduced Bradley Stoughton, who talked on various subjects of interest to members of the Institute, especially the affiliation of local sections with those of other national engineering societies. The minutes of previous meetings were read and approved-and-the Treasurer presented a financial report covering the previous year.

Jan 6, 1918

U.S. Steel Uncovers Massive Iron Ore Deposits in Nevada United States Steel Corporation has confirmed that mineral investigation in Lyon County, Nevada. has been under way since 1960. Confirmation followed press reports of a statement attributed to a Nevada State inspector of mines to the effect that the Corporation has found a major iron ore deposit that may also contain copper ill West Central Nevada. Drillings over the years in a number of locations have indicated extensive iron ore bodie containing a possible quarter of a billion tons of ore of a basically magnetite composition. analyzing less than 40% iron, which would require beneficiation for commercial use. Some of these deposits are deep- lying while others would permit open pit mining. These bodies contain copper in quantities of approxiimately 0.3%. More recent drilling in another area has disclosed evidence of additional deeply-lying deposits of a lower fe content but with more promising indications of copper. A realistic estimate of fe and cu ore reserves cannot be made until more drilling is completed.

Jan 1, 1970

By W. R. Davis

This paper presents a sunimary of the results of a study of the Dornick Hills-Springer sand reservoir of the Velma Pool. Stephens County, Oklahoma. The data are of interest because this type of reservoir is unusual in the mid-continent area. The reservoir is characterized by very steep dips and a relatively thick producing section. Its up-dip productive limit is defined by truncation of the productive sands, and the down-dip limit is defined by deterioration of sand quality rather than by the presence of an oil-water contact. The crude oil is of 29" API gravity, is relatively viscous and was saturated with dissolved gas at the original reservoir pressure. Consideratiqn of the physical characteristics of the reservoir indicates that natural water encroachment will be negligible, and that the producing mechanism will be a dissolved gas drive augmented by gravity drainage. Performance to date tends to confirm this. INTRODUCTION It is the purpose of this paper to present some of the features of the Dor-nick Hills - Springer sand reservoir which are unusual in mid-continent operations. The study was undertaken in an attempt to define the producing mechanism or mechanisms that will control reservoir performance, as an aid in determining well completion and production practices. GEOLOGY The reservoir under consideration is a series of sand bodies of Pennsylva-nian age found in the Lower Dornick Hills and/or Springer formations. For the purpose of this paper, the sand series is referred to as the Dornick Hills-Springer sand. This sand series lies on the northeast flank of the Velma anticline, and dips very sharply to the northeast in TWP 1S-5W, the average dip being about 45º. However, as shown in Fig. 1. the trend of the pool swings eastward in TWP 1S-4W with a coincident de- crease in dip angle. In this portion of the pool the average dip is about 25". Faults in Sections 30-1S-4W and 32-1S-4W are shown in Fig. 1. These faults show only minor displacements for the horizon contoured in Fig. 1, but they do show a pronounced displacement of the immediately overlying beds. Similar faults are thought to exist in TWP 1S-5W; however, since the detailed geological studies necessary to properly define these faults were not available to the author, no attempt to show them in Fig. 1 has been made. The up-dip productive limit throughout the pool is determined by the truncation of the Lower Dornick Hills-Springer sand. The down-dip productive limit does not appear to be defined by edge water, but by a gradual reduction in permeability of the sands. No dry hole has produced a significant volume of water from this sand section. There was a small gas cap in TWP 1S-5W. Most of the wells in TWP 1S-SW encountered an oil sand 70 ft to 150 ft thick, a shale 20 ft to 80 ft thick, and another oil sand 50 ft to 130 ft thick. A few scattered wells in this area encountered other and bodies below these

Jan 1, 1951

By W. R. Davis

This paper presents a sunimary of the results of a study of the Dornick Hills-Springer sand reservoir of the Velma Pool. Stephens County, Oklahoma. The data are of interest because this type of reservoir is unusual in the mid-continent area. The reservoir is characterized by very steep dips and a relatively thick producing section. Its up-dip productive limit is defined by truncation of the productive sands, and the down-dip limit is defined by deterioration of sand quality rather than by the presence of an oil-water contact. The crude oil is of 29" API gravity, is relatively viscous and was saturated with dissolved gas at the original reservoir pressure. Consideratiqn of the physical characteristics of the reservoir indicates that natural water encroachment will be negligible, and that the producing mechanism will be a dissolved gas drive augmented by gravity drainage. Performance to date tends to confirm this. INTRODUCTION It is the purpose of this paper to present some of the features of the Dor-nick Hills - Springer sand reservoir which are unusual in mid-continent operations. The study was undertaken in an attempt to define the producing mechanism or mechanisms that will control reservoir performance, as an aid in determining well completion and production practices. GEOLOGY The reservoir under consideration is a series of sand bodies of Pennsylva-nian age found in the Lower Dornick Hills and/or Springer formations. For the purpose of this paper, the sand series is referred to as the Dornick Hills-Springer sand. This sand series lies on the northeast flank of the Velma anticline, and dips very sharply to the northeast in TWP 1S-5W, the average dip being about 45º. However, as shown in Fig. 1. the trend of the pool swings eastward in TWP 1S-4W with a coincident de- crease in dip angle. In this portion of the pool the average dip is about 25". Faults in Sections 30-1S-4W and 32-1S-4W are shown in Fig. 1. These faults show only minor displacements for the horizon contoured in Fig. 1, but they do show a pronounced displacement of the immediately overlying beds. Similar faults are thought to exist in TWP 1S-5W; however, since the detailed geological studies necessary to properly define these faults were not available to the author, no attempt to show them in Fig. 1 has been made. The up-dip productive limit throughout the pool is determined by the truncation of the Lower Dornick Hills-Springer sand. The down-dip productive limit does not appear to be defined by edge water, but by a gradual reduction in permeability of the sands. No dry hole has produced a significant volume of water from this sand section. There was a small gas cap in TWP 1S-5W. Most of the wells in TWP 1S-SW encountered an oil sand 70 ft to 150 ft thick, a shale 20 ft to 80 ft thick, and another oil sand 50 ft to 130 ft thick. A few scattered wells in this area encountered other and bodies below these

Jan 1, 1951

By LE B. GRAY

ALL meeting of the Chemical Section, National Safety Council, in Rochester, N. Y., put his hand on at least ten salient points that apply to safety in nearly any laboratory ; these are as follows : 1. Impress your laboratory worker at the start that he is dealing with powerful and dangerous-forces and that every experimental set-up must be studied from the stand- point of its fiber, electrical, explosive, and health hazards.

Jan 1, 1929

By Richard S. McCaffery, Joseph F. Oesterle, Oscar O. Fritsche

The method of obtaining the data on which this paper is based is explained in detail in the paper on Determination of Viscosity of Iron Blast-furnace Slags.' The work was made possible by a grant of funds from Engineering Foundation, and it gives the results now obtained, continuing the general subject of our previous work and reported in former papers2 The data experimentally obtained are in the form of a temperature-viscosity curve for any slag of particular composition. (See Fig. 1.) From these curves, the viscosity of a slag of a definite composition and at a definite temperature is taken off and is plotted on a plane triaxial diagram showing compositions of silica lime and alumina on a plane representing constant-magnesia content (Fig. 4). The temperatures at which these results were plotted are 1300°, 1350°, 1400°, 1450°, 1500°, 1550" and 1600" C. and since the constant magnesia plane sections were an even 1 per cent. magnesia apart, magnesia analyses not of even unit magnesia composition were projected to these even unit magnesia planes. For example, 1.78 per cent. magnesia and 2.35 per cent. magnesia were projected to the 2 per cent. magnesia plane. The triaxial diagrams on which this first plotting was made were drawn on celluloid sheets, a transparent material on which it was easy to draw. When all the experimental work was plotted on celluloid in this way, the sheets representing a definite temperature were stacked in the proper order and were examined by transmitted light. Where

Jan 1, 1932

By Arthur La Motte

I NDUSTRIAL explosives, as distinguished from military explosives, include high explosives and blasting powder. The high explosives which are best known are straight dynamite, gelatin dynamite, ammonia dynamite and permissibles. There are two kinds of blasting powder, saltpetre blasting powder and nitrate of soda blasting powder. Blasting powders are mechanical mixtures of nitrate of potash or nitrate of soda with sulfur and charcoal, highly compressed, granulated and glazed. They ignite from a spark and burn with relative slowness, the rate of burning and hence the rate of conversion into gases depending upon the size of the granulation and upon the degree of. confinement under which the powder is placed. High explosives, on the other hand, are chemical compounds which detonate; that is, when the explosive is subjected to a violent shock, provided in practice by a blasting cap or an electric blasting cap, the molecule of the essential ingredient, usually nitroglycerin, is disrupted and the energy and heat released cause any other explosive ingredients which may be present, such as ammoniuin nitrate or T.N.T., to decompose with a resultant evolution of gases at an extremely rapid rate varying from 6000 to 20,000 ft. per second.

Jan 1, 1924

By A. M. Crawford

INTRODUCTION Grouting is an engineering operation which has been practiced for many years and a considerable amount of experience and skill has been developed in this field. However, a review of the current literature (Houlsby, 1982) reveals that the theoretical background and experimental observations that are necessary to adequately predict or describe the performance of a particulate grout (e.g. cement based) in a jointed geologic media are somewhat inadequate. In the near future it is envisaged that the use of grout and grouting techiques will be used to tackle even more difficult problems than have been considered in the past. One problem that is currently being faced by the rock mechanics engineer is the development of geologic repositories for the disposal and containment of high level radioactive waste. In such structures there will be only one opportunity to ensure the success of the containment system. This success will depend to a large extent on the adequate and successful performance of the grout curtains to be utilized around the shafts and shaft liners. Regrouting will not be possible. There are other problems in rock mechanics in which it is frequently necessary to inject particulate media into passages of small dimensions, and where typically the size of fracture being injected is of the same order of magnitude as the particle dimension. For example, in the oil industry in hydraulic fracturing the enhancement of fracture conductivity is maintained by means of proppants introduced into the fracture.

Jan 1, 1984

By I. L. Box

IN planning retreatment of tailings, the material to be retreated should be thoroughly investigated, tak- ing into consideration the total tonnage, the blende content, the specific gravity of the different particles, and the grinding necessary to liberate the mineral. The tailing pile is surveyed by making a closed trav-erse around the outer edges, locating the stations at points from which a considerable portion of the pile is visible. From each of these points the pile is sur-veyed by stadia and a contour map made. The yardage is then calculated from the contour interval and the area inclosed by the contours obtained with a planim-eter. A party of three men can survey an average tailing pile in one and one-half, days. In calculating tonnage it is assumed that 22 cu. ft. of tailing in place equal one ton. Sampling is done by the use of an auger with casing to prevent the hole from caving. These holes may be bored 12 to 15 ft. deep by hand, but to penetrate the entire pile some kind of power is applied to drive the casing and raise or lower the auger. The latter method is more expensive but the increased cost is more than compensated for by the value of the information obtained.

Jan 7, 1928

By Clemens Jones

The difficulties attending the reduction of ferric sulphate in the determination of metallic iron by the method of Marguerite, are often serious, and affect time, patience and accuracy. They depend upon the condition and purity of the zinc used, the state of saturation of the solution, acidity, and temperature. D. J. Caruegie (Chem. News, lvii., No. 1481), says that ferric solutions are instantaneously reduced by the use of zinc-dust. But there are obvious objections to its employment in quantitative work. Dr.

Jan 1, 1889

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Jan 1, 1938

By E. Mille, R. Geffken

The Mg-Si and Mg-Ge phase diagrams were rede-levtnined by thermal analysis, and the existence of a single congruent melting compound in each system was confirmed. The melting points of the two compounds Mg2Ge and ,Wg2Si were found to be 1117.4° and 1085.0°C respectively. The euteclics for the Mg-Ge system occur at 635.6°C (1.15 at. pcl Ge) and 696. 7°C (64.3 at. pct Ge); for the Mg-Si system the eutectics are at 6376°C (1.16 at. pct Si) and 945.6°C (53.0 al. pcl Si). The phase diagrams and known thermodynamic data were used to calculate activity values for both systems. The activities calculated for the Mg-Ge system agreed very well with those previously published. Partial molar enthalpy values for the Mg-Si systetn were calculated from the phase diagram for the composition region where no experimental values have been reported. THE phase diagram for any system is an important source of thermodynamic data. Steiner, Miller, and Komarek1 have derived equations which permit calculation of the activity in binary systems with an inter-metallic compound! if the liquidus and enthalpy data are known. The thermodynamic properties of the Mg-Ge and Mg-Si systems have recently been determined in this by by an isopiestic method, and it was considered that it would be interesting to compare these directly determined values with those computed from the phase diagram. The basic features of the Mg-Ge and Mg-Si systems are essentially similar. The one intermediate compound present in each system. Mg2X, crystallizes in the antifluorite structure and melts congruently. Raynor4 has accurately determined the temperature and composition of the magnesium-rich eutectic in both the Mg-Ge and Mg-Si systems. Klemm and West-linning5 investigated the entire Mg-Ge liquidus, employing sintered alumina crucibles; the purity of the magnesium and germanium starting materials was not reported. The melt was not stirred, and the temperature was automatically recorded to an accuracy of ±3°C. The authors reported large weight changes due to magnesium evaporation between 50 and 67 at. pct Mg. The Mg-Si system has been studied by a number of investigators, and the results have been compiled by Hansen and Anderko.6 Significant discrepancies exist between the two principle investigations of voge17 and Wohler and Schliephake.8 Two different grades of silicon were used by Vogel, one of 99.2 pct purity and the other quite impure, containing 6 pct Fe and 1.7 pct Al. The magnesium purity was not specified. The melts were contained in graphite crucibles with porcelain thermocouple protection tubes under an atmosphere of hydrogen. Samples weighing 10 g were rapidly heated to 50° to 100°C above the liquidus: held, and then rapidly cooled without stirring. Accuracy was ±1 at. pct which is equivalent to a maximum error in temperature of ±18°C. Wohler and Schliephake used 97.9 pct Mg and 99.48 pct Si. The graphite crucibles contained a stirrer and the 15-g samples were melted under an atmosphere of streaming hydrogen. The samples were chemically analyzed after each run. Because of the scarcity of the data, the impurity of the starting materials, and the resultant uncertainty and inconsistency in the published liquidus values, it was decided to undertake a reevaluation of the Mg-Ge and Mg-Si phase diagrams by thermal analysis. EXPERIMENTAL PROCEDURE Alloys were prepared from 99.99+ pct Mg (Dominion Magnesium Ltd.) with impurities in ppm: 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu. <10 Fe; 99.999 pct Ge (United Mineral and Chemical Corp.), and 99.999 pct Si (Wacker Chemie Corp.). All graphite parts were machined from high-density (1.89 g per cu cm) G-grade graphite obtained from Basic Carbon Corp. with a total ash content of 0.04 pct. Boron nitride parts were machined from rods of National-grade H.B.N. boron nitride. All graphite and boron nitride pieces were baked out under running vacuum at 1100°C for 24 hr before us Cylindrical graphite crucibles (1; in. OD, 23/4 in. long, l3/8 in. ID) were tightly closed with threaded graphite covers which had 21/4-in.-long thermocouple wells and 1/4-in.-diam off-center holes for stirrers. The cover and thermocouple well were machined from a single piece of graphite. A stirrer was made from a flat cylindrical graphite plate perforated with five 3/16-in.-diam holes and a 1/2-in.-diam central hole, and was held parallel to the crucible bottom by a 1/4-in.-diam. 4-in.-long graphite rod which screwed into the plate and extended up through a tightly fitting hole in the crucible cover. An iron core enclosed in a glass capsule was attached to the stirrer with an 18-in.-long molybdenum wire, so that the stirrer could be magnetically raised and lowered from outside the system. One crucible and stirrer with essentially the same dimensions given above was made entirely of boron nitride. Chunks of magnesium were premelted, cast into 11/2-in.-diam. rods, and then cut into lengths varying from a to 1 in. A 5/16-in. hole was drilled through the center of each piece to accommodate the thermocouple well and the individual pieces were then cleaned and rinsed with acetone. The total weight of an alloy was 50 to 70 g in the Mg-Ge system and 40 to 60 g in the Mg-Si system. The pure components were weighed to an accuracy

Jan 1, 1969

By Charles J. Haas

The resistance which rock bolts offer to shear movements along fracture planes and bedding planes near a mine opening has been suggested as one of the mechanisms by which bolts contribute to the support of weak rock in the roof or sidewall. That such displacements do occur is a fact fairly well known. Inspections of drill holes that have been drilled for some time often reveal that the holes have been offset at one or more points some time after drilling. Resin grouted bolts are often cited as being better able to resist shear movement in the roof because the annulus around the steel bar is filled with grout, whereas the sides of a conventional bolt will not contact the rock until a rather large shear displacement has occurred. When this project began, there were no experimental data to support or refute the above arguments. A laboratory shear test program was, therefore, devised to evaluate the effectiveness of various types of bolts in resisting shear under various conditions which exist in situ. Research reported earlier (Haas, 1976) included a theoretical analysis of a conventional bolt intersecting a shear surface, and experimental data on the shear resistance of smooth (lapped) shear surfaces, intersected at various angles by conventional and resin grouted bolts. The present paper extends the previous analysis to consider the effect of the initial roughness of the shear surface. Joint roughness is a particularly significant factor since undulations of the shear surface cause dilatation of the joint, which in turn, causes high tensile loading of a bolt intersecting the joint.

Jan 1, 1982

Greater automation of facilities is probably the best hope of the mining industry in its efforts to surmount continually rising labor costs. Underground mining, with its inherently low unit labor output, is especially vulnerable to rising costs, and here maximum automation is becoming increasingly important. One area of such operations that has been receiving a great deal of investigation is that of ore haulage and hoisting, two steps that often account for 10-35% of underground operating costs. Innovations and experimentation by mining firms and manufacturers over the past few years have resulted in larger, faster and more efficient tramming and hoisting equipment, but the White Pine Copper Co., at its operation in the Upper Peninsula of Michigan, is preparing to start up an entirely new concept in haulage later this summer. Known as the Dashaveyor System, it consists of individually powered modules (cars) that run on tracks inside a rectangular tube or on an open trackway at predetermined speeds up to 50 mph. At White Pine the Dashaveyor will be used to carry ore (crushed underground to -10 in.) from the mine to the concentrator. Dr. James Boyd, president of Copper Range Co., which is a 25% shareholder in The Dashaveyor Co., has indicated that if the Dashaveyor meets the expectations for surface operation, it will also be used underground for ore transport in place of the several miles of conveyor belts currently in use (Business Week, July 29, 1967).

Jan 7, 1968

By M. Hansen, C. C. Wang

THE 6 phase of the Cu-Sn system (Cu,Sn, = 32.53 pct Sn) was considered to be stable down to room temperature until Owen and Iball showed by X-ray analysis that it undergoes a eutectoid decomposition into the a and e phases at a temperature near 300°C. Their findings have been confirmed by other investigators,2-5 a11 of whom used X-ray diffraction studies of powdered specimens. The transformation temperature has been reported by various authors as lying between 300" and 380°C. To our knowledge, no microscopic evidence of the eutectoid reaction has been published, as yet. It was in connection with other work that longtime annealings at 300°C were conducted with alloys containing 22, 32.6, and 35 pct Sn (nominal compositions) prepared from electrolytic copper and electrolytic tin and cast in a small iron mold. The specimens were first annealed at 700°C for 5½ hr and quenched from 400 °C after cooling to, and annealing at, that temperature for 9½ hr. After this treatment the sample with 22 pct Sn was cold worked for 15 pct reduction in thickness; the 32.6 and 35 pct alloys were too brittle to be cold worked. The final anneal at 300°C was done in a sealed pyrex glass bulb for 63 days. Fig. 1 represents the microstructure of the annealed alloy with 22 pct Sn. It shows primary a solid-solution crystals in a matrix of the (a + 8)-eutectoid formed at 520 °C. The a crystals contain 8 inclusions which precipitated from a due to the decrease in the solubility of tin in copper with fall in temperature. The decomposition of the 8 phase into a (light) and E (dark) can clearly be seen in some areas of the (a + 8)-eutectoid matrix. However, the decomposition is far from being completed, even after the long-time anneal used. Figs. 2 and 3 depict the microstructures of the annealed 32.6 pct alloy, which was intended to consist entirely of 6 phase. Due to some loss in copper on melting, the composition is slightly higher in tin. Accordingly, the sample after quenching from 400 "C consisted of grains of the 8 phase with the e phase arranged along the grain boundaries and as a Wid-manstatten precipitate within the 6 grains. After an annealing time of 63 days, the eutectoid decomposition, 6 + a + e, is still in its early, initial state. The pearlitic type of eutectoid is nucleated at the c crystals, preferably those surrounding the grain boundaries of the 8 phase. The appearance of the (a + €)-eutectoid in the 35 pct Sn alloy was very similar to that shown in Figs. 2 and 3. Again, the eutectoid decomposition nucleated at the 6 phase and proceeded from there into the 8 areas. As is evident from Fig. 2, the rate of decomposition of the 6 phase at 300°C is extremely sluggish: In the representative area shown only about 5 pct of the 8 phase has undergone the eutectoid trans- formation after annealing for 63 days. On the other hand, Owen and Williams2 have reported that X-ray photographs of powdered samples with between 17.5 and 34 pct Sn did not show 8 lines after annealing for only five to seven days at 300°C. This is in accordance with the fact that the rate of reaction in powdered samples is higher than in massive specimens, as a result of the excess free energy of the powder (due to its greater surface area). The authors wish to express their thanks to C. A. Johnson for preparation of the micrographs.

Jan 1, 1952

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors&apos;-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969