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By C. Richard Tinsley

Like most minerals, coal is inherently a demand-limited commodity. The very sedimentary nature of its occurrence implies greater availability potential than demand. But this situation is overridden by economics among fuels, between coals, and within coal blends. Such considerations make coal forecasting a very hazardous profession indeed. THERMAL COAL If one thought that the lead times involved with a mining project were very long, one has obviously not been exposed to the planning process in the electric generation business - a process seriously confounded by shifts in load growth, environmental pressures, capital intensity, security of fuel sourcing, inter-fuel economics, and so on. But as a general rule, the near-term forecasts for thermal coal can reliably be based on a bottom-up, plant-by-plant analysis. Cement plant conversions can also be reasonably estimated next in order of reliability, although they have a much wider spectrum of coal qualities and fuel sources to choose from with a notably higher tolerance for sulfur and ash. Finally, industrial demand can be assembled from the estimates for conversions by pulp/paper plants, chemical plants, etc. The industrial sector is harder to estimate, since it may involve small boilers or dual-fired units. Assessing demand in the Pacific Rim is relatively a straightforward process in the near term because the major importing countries are all located on the Asian continent with either negligible or very minor (yet stable) indigenous coal production, (itself often operated on a subsidized basis). Furthermore, all imports are seaborne. These major importers are Japan, Korea, Taiwan, and Hong Kong with Thailand, Singapore, and Malaysia up-and-coming consumers. The suppliers to this market all have substantial reserves to back up decades of exports to these countries. Australia, the US, Canada, South Africa, China, and the USSR dominate the supply side. The second oil-shock of 1979/1980 has convinced the importers that reliance on oil can be expensive and eminently interruptible. Thus, they are determined to diversify away from oil' to nuclear and coal for generating electricity and for coal for other purposes where possible. This trend is seen to continue even in the face of the oil glut worldwide and oil-price reductions in early 1982. But the importers are also convinced that reliance on one coal source and, in particular, one infrastructure route for the coal chain from mine to consumer can be equally expensive and interruptible. Strikes in the US and Australia; excessive demurrage at certain ports; relegation of coal to a lower priority on multiple-use railroads in the USSR and China; and concern over escalation on high-infrastructure or high-freight coal chains are among the risks worrying the importers. As a consequence, Pacific Rim thermal coal purchases are being allocated among supplier nations, between ports, and within each country. An example of Japan's shift away from Australia and toward the US and Canada is shown in the estimates in Table 1. But the confidence of the import estimates deteriorates sharply beyond the plant conversion timetables and construction schedules in the near term. If part of the second generation of coal-fired power plants can handle lower-energy coals, the field of suppliers could widen to accept sizeable tonnages from Alaska, Wyoming, Alberta, or New Zealand resources. These supply sources generally have some infrastructure or freight advantage to compensate for their lower quality and to compete on a delivered energy-unit basis. These also offer diversification in sourcing. And the possibility of coal liquefaction in Japan further widens the sourcing network. A great number of Pacific Rim coal forecasts have been generated, especially for Japanese thermal-coal imports which are expected to grow strongly in the 1980's. Since the Japanese themselves have not yet settled their energy policy, the exact numbers are hard to call. Nevertheless, at 50 million tonnes of imports in 1990, Japan would consume 50-60% of the total Asian thermal coal imports as shown on Tables 2 and 6. The next most important consumers are the "island" nations of Korea, Taiwan, and Hong Kong (see Tables 3-5). All three are embarking on power plant developments usually with captive unloading facilities, capable of accepting more than 100,000-dwt vessels. Korea, with no-indigenous bituminous coal, is not especially enamoured with US coals, which are deemed too heavily loaded by freight and infrastructure costs -- up to 70% of the delivered price. Thermal coal contracts are presently split to Australia (70%) and to Canada (30%). Korea Electric Power Co. is already considering second-generation boilers capable of burning lower-quality coals than the present standard. Korea does burn domestic anthracite.

Jan 1, 1982

By J. P. Dunlop

THE fact is notable though probably little known that the United States is the only nation obtaining and distributing through its Government bureaus any data pertaining to waste metals and drosses. Some foreign governments do issue reports relating to mine or smelter production of primary metals, but none gives in scope and detail the information published now by the U. S. Bureau of Mines and formerly by the U. S. Geological Survey; and this is despite the fact that the funds annually allotted for those purposes are insignificant in comparison with allotments for the preparation of data relating to other industries of like importance. The earliest data on the production of metals from secondary sources in the United. States were contained in a press bulletin issued by the U. S. Geological Survey on Jan. 4, 1909. The information published was that for the year 1907 obtained and compiled by C. E. Siebenthal, who was one of the first to visualize the growing importance of the scrap-metal industry. The National Conservation Commission had emphasized its opinion that the known domestic supply of certain kinds of the more important metals was being rapidly marketed and that while there was no immediate cause for concern it was best to conserve such resources. Not only had there been a lamentable lack of any data regarding the quantity of scrap metals available or used but also gross carelessness and indifference in the segregation, collection, and effective use of scrap material. Siebenthal realized that even approximately correct statistics of recoveries from the more important base-metal scrap and drosses were nearly as essential to both producers and consumers as the statistics of the output of primary metals. There were not then nor are there now sufficient funds for complete collection of data, nor was it considered the province of the Geological Survey to do more than determine approximately the recovery of secondary metals for use in supplementing those given for the primary metals. Undoubtedly the first bulletins issued did not give the full output, for it takes time to establish contacts for an inquiry covering so

Jan 1, 1928

By J. B. Mackintosh

In a recent paper read before the Institute on this subject, Mr. G. C. Stone advances the theory that the precipitate obtained in Williams's volumetric process,* by treating the boiling nitric acid solution of a manganese salt with potassic chlorate., is not pure MnO2, but approximates more closely to the composition 10Mn02+Mn0. As the value of the process and the accuracy of our results mould depend on whether this was the fact or not, it has seemed to me, and to my associates, Messrs. Beebe and Colly, that it would be of importance to ascertain the composition of this precipitate, and to that end the following series of experiments has been undertaken. These experiments have all been based on the considerations: 1. That potassic permanganate has an oxidizing power equivalent to five atoms of oxygen for every two of manganese : K2Mn2O8 = K2O.2MnO.O5. 2. That the same amount of manganese in the state of binoxide has an oxidizing power equivalent to two atoms of oxygen : 2MnO2 = 2MnO.O2. If, then, we take a solution of permanganate of unknown strength, and reduce it to binoxide, the oxidizing power of the binoxide formed will be equal to that of two-fifths the quantity of the permanganate solution originally taken. While, if the precipitate obtained should not be binoxide, but an indefinite or definite mixture of bin- and mon- oxides, then, from its equivalent oxidizing power, we can calculate its composition. The analyses were conducted in the following manner. The amount of permanganate taken was decomposed with hydrochloric acid, and concentrated to expel the excess of water. Sufficient excess of nitric acid was now added, and the solution was boiled until all the hydrochloric acid was destroyed. The manganese was then precipitated by potassic chlorate; and, after standing some time to cool—a pre-

Jan 1, 1884

By A. G. Metcalfe

THE failure to detect any change in the thermal properties of cobalt at the Curie point would appear to indicate that the apparatus may have a limited sensitivity. The Curie temperature has been determined by direct methods to be 1121+3°CP and 1131°C.3 The specific heat has been determined many times'.' and weighted values are given in Table I. The allotropic transformations in iron and titanium, used by the authors to test the experiment method, involved a volume change of the order of 3 pct on going from the close-packed to the body-centered-cubic lattice. These energy changes are likely to be much larger than those involved in a diffusionless transformation from a hexagonal to a cubic-close-packed lattice. However, it has been pointed out that thermal observations are unreliable in the detection of phase changes when these are near a Curie point.' James 0. McCaldin and Pol Duwez (authors' reply)—The sensitivity of the present technique is limited to first-order transformations, so that gradual changes in specific heat, e.g., in the vicinity of Curie points, are not detected. Furthermore, the existence of first-order transformations with latent heats much smaller than those occurring in the known allotropic transformations of iron and titanium is, we agree, still pending.

Jan 1, 1956

George L. Heath, South Lake Linden, Mich. (communication to the Secretary): In presenting some notes on the "Heine's Blue Test" Mr. Smith expresses a preference for fresh standards and a cheaper bottle; but this is rather a reversion to the old method, since I devised in 1897 the newer method of preparation and preservation of' permanent standards, which were not used with any success in the original method. Many busy western assayers no doubt value a method for preparing a permanent set of standards in air-tight glass-stoppered bottles, whose use brings the method as near perfection as one could desire as regards rapidity of color-reading and avoidance of unnecessary work. Mr. Smith notes that his color-readings were compared with an electrolytic assay of another ore-sample, and that my electrolytic assays were made on the " blue test" solution from colorimetric assay. He omits, however, reference to the fact, showing the advantage of my procedure, that the next column in table of

Jan 1, 1901

By H. Evans, L. A. Hunt

The raw materials used in the blast furnaces at the Geneva Works of U.S. Steel Corp. have a high degree of variability in size-consist and chemical content. To overcome the problems caused by the use of highly variable raw materials in the blast-furnace operation, large blending piles are used. An investigation of the blending system showed that variability was significantly reduced by the use of these blending piles. This paper describes the blending system, the method used to evaluate the effect of the blending system, and the results of the investigation. The remarkable improvement in blast-furnace performance since World War II has been in large measure due to the use of beneficiated burdens to reduce the variation of both chemical analysis and size consist. This practice allows the operator better control of his blast furnace, enabling him to operate more economically and to produce chemically uniform hot metal. Planning for uniformity usually begins during mining by extracting ore from several locations within a pit to produce a final product with a specified analysis. Another approach is to stockpile ores having widely varying analyses in individual piles and then drawing the required amounts from each stockpile to provide a blend with a predetermined analysis. A further improvement in blending procedures is to take ores from several sources, bedding them horizontally in layers and reclaiming by vertical slicing from the blended pile. The last procedure, when properly executed, is one of the best methods for achieving maximum uniformity with highly variable ores. U.S. Steel Corp.'s Geneva Works initially obtained iron ore for their blast furnaces from the Cedar City area of southern Utah. These ores were formed primarily by the replacement of limestone and siltstone formations with solutions containing iron and several other elements. The original iron content of the ores in the ground varied from a high of 70% to practically zero with a minimum acceptable iron content for shipping of 37%. Substantial amounts of silica, calcium, magnesium and alumina were found in the ores along with minor amounts of copper, lead, zinc, nickel, titanium, manganese, phosphorus and sulfur which were sometimes present in detrimental amounts. Iron-to-silica ratios varied considerably throughout

Jan 1, 1968

By C. H. Li, R. J. Stokes, T. L. Johnson

The effect of alumina particles on the nucleation and growth of cracks through a silver- chloride matrzx has been investigated. It has been found possible to promote fibrous cracking in dispersion-strengthened silver, chloride under notch-impact conditions at temperatures at which silver chloride alone cleaves brittlely The modification) of fracture beIzavzor is thought to be due to the relaxation of hydrostatrc stress beneath a notch by the nucleation of cavities near alumina particles. In recent years, composite or dispersion-strengthened materials have been studied primarily to understand their high resistance to plastic flow particularly at elevated temperatures. Dislocation models have been developed with which it is possible to deduce with fair success the effects of interparticle distance, particle size, temperature, upon yielding and creep behavior.l-4 Much less attention has been paid to the fracture behavior of these materials (with the notable exception of common structural steels) and little is known experimentally about the manner in which inclusions affect the nucleation and growth of cracks through a matrix. Nevertheless a beginning has been made in connection with fibrous cracking in ductile matrices where inclusions appear to play an essential ro1e.5-7 During the severe localized plastic deformation which accompanies necking in a tensile test, cavities are believed to develop at inclusions; these cavities subsequently grow and coalesce by plastic flow until separation is complete. It is of interest to consider whether inclusions can affect fracture behavior under loading conditions which restrict the plasticity of the matrix itself (for example, cleavage under conditions of a high imposed strain rate at low temperatures). It is particularly interesting to study these effects in a solid which shows a spectrum of behavior ranging from fully ductile to semi-brittle behavior. Such a solid is silver chloride whose mechanical behavior depends sensitively upon temperature and strain rate.'," The present paper is concerned with a study of the influence of inclusions (in the form of alumina particles) on the fracture behavior of silver chloride loaded uniaxially at low strain rates at room temper- ature and also under notch impact conditions over a wide range of temperature. In particular, it will be shown that the alumina particles can exert a startling effect on the ductile-brittle transition temperature of notched silver chloride and that the magnitude and nature of the effect depends upon both the quantity of alumina and the shape of the alumina particles. 1. EXPERIMENTAL PROCEDURE 1.1 Materials Used. Silver chloride powder of analytical reagent (AR) quality having an average particle size 6 was supplied by the Mallinckrodt Chemical Works (st. Louis, MO.). Acid washed 900 mesh alumina powder, designated A38-900, was supplied by the Norton Co. (Cambridge, Mass.). This powder was added to silver chloride in two forms: a) the as-received condition in which the individual particles were of random irregular shape; their statistical average size was 7; b) in a condition in which each particle was spherically shaped by a fusion technique. In this case, the statistical average particle size determined with the optical microscope was approximately the same (about 5p) but electron micrographic evidence indicated that many ultra fine particles were present in the spheroidized powder. 1.2 Preparation of Composite Materials. Silver chloride-alumina composites containing 2.5, 5, and 15 pct by volume of alumina were produced by the extrusion of mechanically mixed powders blended in a ball mill for 24 hr at room temperature. The mixtures were compacted at 50,000 psi at room temperature in the form of billets 3/4 in. in diameter and 1 in. long which were then extruded with a 16:l reduction ratio at 370°C through a radius-type steel die having a 5 deg lead-in angle. An extrusion temperature of 370°C was selected to ensure that all composites had sufficient plasticity to be extruded. Apart from this general requirement, the choice was arbitrary. 1.3 Microstructure of Composites. Attempts were made to check the distribution of alumina metallo-graphically by polishing transverse and longitudinal sections of the extruded rod. Specimens were wet-ground to 600 emery paper and lapped successively with 5 and 0.25-p grades of diamond paste. They were etched for 10 sec in 10 pct sodium thiosulfate solution and lightly polished in concentrated ammonium hydroxide. The most effective way to render the alumina particles and grain boundaries visible was to radiate the surface with intense white light to decorate the grain boundaries and the particle-matrix interfaces photolytically.

Jan 1, 1962

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0'Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

By S. W. Ross

In 1936 a description of the plant (Fig 1) and process employed by the Electrolytic Zinc Co. of Australasia Ltd. for the recovery of zinc from zinc concentrate by the electrolytic process was prepared. † During the twelve years which have elapsed since the preparation of the earlier paper, several major changes in the metallurgy of the process have been introduced. It is the purpose of the present paper to give a general description of these changes and thus to bring up to date the description of the plant and process. Summary The major changes in Risdon practice since 1936 have been: 1. Replacement of two stage roasting by a preliminary roast followed by the flotation of all the leach residue and the roasting of the flotation concentrate. 2. Screening of all calcine fed to the pachucas. 3. Continuous leaching of calcine and improved classification of pachuca discharge. 4. Close control of hydrogen ion concentration during purification for iron removal. 5. Recovery of cobalt as a good grade oxide. 6. Production of part of the zinc output in the form of "four nines" metal (99.99 pct purity). 7. Closer spacing of electrodes thus increasing the potential output of cathode zinc per cell by 50 pct. Changes which are in prospect and for which construction work is proceeding at the present time involve the starting up of: 1. Two suspension roasters. 2. A contact acid plant to produce 150 tons‡ of acid per day and replacing the existing Mills Packard chamber plant. 3. Extra power station capacity to permit greater current flow to existing cell room units. This will increase the output of cathode zinc from about 245 to 290 tons per day. Plans for the future envisage the building of an ammonium sulphate plant, the first unit of which will produce about 50,000 tons per year, and improved treatment of zinc plant residue for the recovery of zinc, lead and other metals. At the end of this paper tables of metallurgical data are presented relating to the year ending June 30, 1948. Details of Changed Practice Output In 1936 the production of cathode zinc amounted to about 200 tons per day. This has since been increased to about 245 tons per day while plant extensions are practically complete which will permit of an output of about 290 tons per day in the near future. Roasting Division ROASTING POLICY A major change has occurred in the roasting policy. Twelve years ago the method in use was to carry out a two stage roast in the first stage of which sulphide sulphur was reduced to about 6 pct. The pre-roast calcine was re-roasted in modified Leggo furnaces using coal as fuel, sulphide sulphur being reduced to about 0.8 pct. The whole procedure was described on pp. 482491 of the earlier paper. Although this roasting procedure had certain advantages it possessed some distinct disadvantages. For instance, it appeared uneconomical to heat up the entire input of pre-roast calcine to roasting temperature by the expenditure of fuel in order to oxidise a few percent of sulphide sulphur. It was argued that if the pre-roast calcine were leached and a process could be developed for the recovery of a zinc sulphide concentrate from the leach residue, this concentrate, small in weight compared with the pre-roost calcine, would probably roast autogenously, thus virtually eliminating the expenditure of fuel as well as greatly increasing the weight of sulphur oxidised per square foot of furnace hearth area. The obvious method of producing a suitable concentrate from leach residue was by flotation. It will be recalled (see p. 495 of the earlier paper) that when two-stage roasting was practised the leach residue was classified, the granular fraction was ground and floated while the slime fraction was thickened, filtered and dried ready for shipment to a lead smelter. This process worked quite successfully. However, when trials were made of leaching a calcine carrying several percent of sulphide sulphur the granular fraction still floated well, but the slime fraction carrying 8-10 pct sulphide sulphur yielded very poor results when subjected to flotation. This fact held up the application of "pre-roast" leaching for many years. However, successful flotation of the slime fraction of leach residue was finally achieved and in August 1940 the slime flotation plant began operation, while the leach-

Jan 1, 1950

By W. A. Tiller, W. C. Johnston

A high-temperature electromagnetic stirrer is described in which heating and stirring are accomplished by independently controlled power sources. The appavatus is suitable lor use at temperatures up to 1700°C in a variety of ambient atmospheres. Some typical examples of the homogenizatimz capabilities of the system are given. THERE are few processes in solidification that are not markedly affected by motion in the melt during freezing. In many instances, the mechanisms are diffusion-controlled, and the transport in the melt may be greatly accelerated by deliberately stirring the melt. In zone-refining, stirring1 assists the removal of rejected impurities from the interface, so the process proceeds at a faster rate. The transition from a planar to a cellular interface is caused by constitutional undercooling in the melt ahead of the interface: and stirring delays its onset. Stirring is valuable for homogenization of melts: and chemical reaction with sluggish kinetics may be accelerated. Finally, it has been observed that grain refinement is related to motion in the melt. Fine grain castings are usually produced by the addition of catalysts to the -melt,' catalysts which are thought to act simply as hetereogeneous nucleation centers. Even here motion is important. Richards and Rostoker 5 applied ultrasonic vibration to a solidifying A1-Cu alloy which had been innoculated with a catalyst and found that the grain diameter fell linearly with the amplitude, the peak acceleration and the power input to the melt from the transducer. Finally, mechanical and electrical stirring alone have been used to generate a fine-grained structure.6,7 Johnston ef a1.' have carried out a series of systematic investigations of grain refinement by electromagnetic stirring in a number of low melting point alloys. They found, for example, that the number of grains per unit volume in Pb-Sn alloys could be increased several orders of magnitude by stirring an undercooled melt at the moment of recalescence. In general, a relation AT .H = constant prevailed for a given grain size, where AT was the undercooling of the melt and H the field strength. In more recent work, deliberate homogeneous nucleation of slightly undercooled melts established that the mechanism of refinement must be one involving crystal fragmentation and subsequent multiplication, rather than a "shower" of nuclei effect.9 It is the purpose of this note to describe a stirring device suitable for use up to 1700°C. At low temperatures mechanical stirring and direct-current methods are feasible, but at high temperatures the problem of a protective atmosphere and of electrode corrosion rules out such procedures. The most convenient method for high temperatures is to use externally generated ac fields for both stirring and heating. With rf induction heating alone, considerable stirring and agitation can be achieved, but in general the penetration of field into the melt is small, and the stirring cannot be controlled independently of the heating. In the present experiments, separate power sources of different frequencies for heating and for stirring were used. A susceptor design was chosen so that the 450 kc rf heating field was completely absorbed in the susceptor. The stirring frequency, 400 cps, hereafter called the af field, was chosen so that a high penetration of the melt proper was achieved. EXPERIMENTAL APPARATUS The apparatus, Fig. 1, consists of a quartz tube and end plates, surrounded by an rf induction coil and six equally spaced af stirring coils, four of which are shown in full and a fifth in section. Each af stirring coil is a transformer of which the secondary is a single-turn water-cooled copper loop and the primary is composed of two 10 amp-117 v Variac cores as shown. These cores are cooled by forced air, as each of the six pairs will carry maximum currents of 15 amp for short periods. Each set of Variac windings are connected in series, but opposite sets are connected in parallel with a three-phase 400 cps 400-v source. By properly phasing the coils in this way, a rotating field is produced. Capacitors C1, C2, and C3 in Fig. 2 are used to match this inductive load to the generator. Fig. 3 shows a cutaway view of the quartz tube. The sample (1 in. diam by 1 in. high) is placed in a tapered alumina crucible. An axial W-26 pct Re thermocouple, enclosed by a protection tube, is provided. The cruci-

Jan 1, 1968

By W. S. Hyler, L. W. Berger, R. I. Jaffee

Hydrogen additions of 390 ppm to A-55 titanium and 368 ppm to Ti-8 pet Mn have no deleterious Hydrogenadditionseffect on the unnotched and notched rotating-beam fatigue properties of these materials. 'These amounts of hydrogen, however, are sufficient to cause severe notch-impact thesematerials.embrittlement in A-55 titanium and pronounced loss of tensile ductility in Ti-8 pet Mn. The lack of embrittling effect in fatigue in the latter alloy is consistent with the postulated strain-aging mechanism of hydrogen embrittlement in a-ß alloys. There is a significant strain-agingincrease in the unnotched endurance limit of A-55 titanium with the addition of hydrogen. This increase may be explained as the result of internal heating effects which would dissolve the hydride and cause solid-solution strengthening. TITANIUM and its alloys may be seriously embrittled by relatively small amounts of hydrogen. The form which this embrittlement takes has been shown to vary with alloy type. The a alloys, for example, suffer most strongly from loss of notch-bend impact toughness' when sufficient hydrogen is added, and this effect has generally been associated with the presence of hydride phase in the micro-structure. In a-ß alloys, on the other hand, hydrogen is most detrimental to tensile ductility in slow-speed tests,2-1 and the embrittlement may be detected in a most convincing manner by means of rupture tests at room temperature. This particular kind of embrittlement has not been associated with a change in microstructure, but has been classified rather generally as associated with a strain-aging type of mechanism.' In the present paper, the effect of an embrittling amount of hydrogen on the rotating-beam fatigue properties of both an a and an a-ß titanium alloy is covered. For this study, annealed commercially pure (A-55) titanium was chosen as an a alloy, and equilibrated and stabilized Ti-8 pet Mn as representative of a typical a-ß alloy. Nominal hydrogen levels of 20 and 400 ppm were evaluated, the latter amount having been shown previously to be severely detrimental to the impact toughness of commercially pure titanium and to cause pronounced strain-aging embrittlement in the Ti-8 pet Mn alloy. The only report of the effect of hydrogen on the fatigue properties of titanium is given by Anderson et al.,° in which a push-pull type of fatigue test was conducted on as-received commercial-purity titanium sheet. Much scatter was found in the results, but generally the presence of hydrides slightly decreased the fatigue strength of unnotched specimens in the longitudinal direction. The results of notched tests were masked too greatly by scatter to be significant. Experimental Procedure Preparation of Materials—Analyses of the A-55 titanium and the Ti-8 pet Mn alloy used in this investigation are given in Table I, which indicates the 8 pet Mn alloy to be more nearly a 6 pet Mn alloy. This alloy will be referred to as Ti-8 pet Mn, however, since this is the commercially designated composition. Both alloys were received in the form of5/8-in. diam rod and, after suitable surface preparation, 5-in. lengths were vacuum annealed at 820°C. Half of the rods for each material were then hydrogenated at 820°C to a nominal hydrogen content of 400 ppm. The hydrogenated and vacuum-annealed A-55 rods were hot swaged at 700°C from 5/8-in. diam to 1/4-in. diam, and then annealed 1 hr at 800°C and air cooled prior to preparation into test specimens. Fabrication of the Ti-8 pet Mn alloy was by hot swaging to 3/8-in. diam at 760" and then 1/4-in. diam at 704°C. This material was then annealed 1 hr at 704", followed by furnace cooling to 593"C, and finally air cooling to room temperature. Evaluation—In order to examine more completely the effects of hydrogen on the particular materials studied, slow-speed tensile and notch-bend impact properties were determined in addition to fatigue data. Tensile specimens were of the standard ASTM type with a reduced section of 1/8-in. diam and a gage length of 1/2 in. A subsize cylindrical Izod specimen was used for impact tests. These specimens had a 45" notch with a 0.005-in. radius and a 0.150-in. root diam, and the stress concentration factor of this notch in bending was Kr = 3. Both the ten-

Jan 1, 1959

By B. Chalmers

THE practical importance of the phenomena of melting and freezing must have been recognized for a very long time. The difference between ice and water, for example, has had a profound influence on the history of mankind and the evolution of society. The possibility of melting a metal and allowing it to freeze in a mold of chosen shape has been an essential ingredient in our mastery of the art of shaping metals, and therefore in the evolution of the: machine age in which we find ourselves. The importance of melting and freezing, as applied to metals and alloys, has been so great, in fact, that empirical solutions have been found for the multitude of practical problems that have arisen. This approach has been so successful that relatively little attention has been directed to arriving at an understanding of the fundamentals of the processes. But metallurgy has come to a stage at which we may expect that some, at least, of the more complex problems that have not yet been solved (or perhaps even recognized) may be handled more effectively by scientific study, theoretical understanding, and logical experimentation than by trial and error. In this lecture, therefore, I propose to describe in outline what I think really happens when a metal freezes. In doing so I hope to explain many of the phenomena which have been observed, and in particular to account for the structures that are obtained in actual ingots and castings. The basic problem, to which this lecture represents a tentative partial answer, is this: a mass of metal, containing known proportions of various elements, is melted, heated to a given temperature, and then allowed to freeze under specified conditions. What will be the "structure" of the resulting metal? The term structure includes: 1—crystal size, shape, and orientations, 2—distribution of chemical elements, and 3-—shape, including cracks, cavities, pores, etc. The Solid-Liquid Interface We will first consider what takes place if a single crystal of a metal in the form of a rod is heated, not uniformly, but so that one end is hotter than the other. If this heating process is continued long enough, the hotter end will eventually melt; we will suppose that the rod is in a containing vessel so that the molten metal does not run away, Fig. 1. When some of the metal has melted, we have some solid, some liquid, and an interface or surface of contact between them. If the source of heat is now removed, the interface will move so that some of the liquid freezes, and if the supply of heat is suitably adjusted the interface will remain at rest. This very simple arrangement allows us to study the basic processes of melting and freezing, and if we fully understand this simple case, we may be able to account for what takes place under practical conditions where the heat does not all flow in the same direction, and where the heat flow is determined not by a controllable source of heat but by the heat capacity and temperature of metal and mold, and by the heat loss from the mold surface. The solid-liquid interface is evidently the region of the greatest interest to us; on one side of it there is crystalline solid, and on the other, liquid. In the solid, each atom has a well defined position, around which it vibrates as a result of thermal agitation. It only leaves this position in the relatively rare event of a "diffusion jump." The liquid is much less systematically organized. The atoms are about as far from their neighbors as in the solid, but the arrangement is much less systematic and is continuously changing. The solid and the liquid are represented diagrammatically in Fig. 2. The average energy of the atoms in the liquid is greater than in the solid by an amount that corresponds to the latent heat of fusion, i.e., the amount of heat that has to be supplied to convert unit mass of solid into liquid at the same temperature. The Two Processes As has recently been shown by Jackson and Chalmers,3 many of the features of the processes of freezing and melting can be understood if it is assumed that a continuous and rapid interchange of atoms between solid and liquid always takes place at a solid-liquid interface." It is necessary to con- sider two distinct processes, that of melting, in which atoms leave the surface of the solid and become part of the liquid, and the converse process,

Jan 1, 1955

By W. L. Saunders

When work was begun in September, 1910, on the rock excavation for the foundation of the gigantic dam at Valhalla, N. Y., which is to convert Kensico lake into an important storage reservoir of the Catskill Aqueduct system, one of the first steps taken by the contractor, H. S. Kerbaugh, Inc., was the development of a quarry to supply the stone needed in the

Jan 1, 1915

By S. H. Cathcart

Price, production and drilling operations exceeded any year since 1930. A top price for crude of $2.55 was maintained from May 1 to November 6 and increased activity about coincides with that period. The average crude price for the year was: Bradford, $2.46; Kane-Butler, $2.34; Southwest Pennsylvania, $2.13. Production for the year exceeded 15 million barrels, an increase of about 2 million barrels over 1933. That this increase was more than justified by market demand is indicated by a reduction of 892,000 bbl. in stocks for the year. Two classes of data appear on Table 1, which are differentiated by footnote references. Where possible the .figures were obtained from individuals and companies that, from long acquaintance and varied contacts, are most capable of supplying an estimate where an estimate is necessary. The remaining data represent a rather careful compilation from all available published records (see p. 378). Drilling operations and production as summarized by the Oil City Derrick are as shown on Table 2.

Jan 1, 1935

By B. G. Matson, M. A. Whitfield, G. R. Dysart

This paper describes the development of u computer program to calculate changes that occur in the length of tubular goods due to temperature and pressure changes during stimulation operations. Due to the numerous variables involved and the uncertainty of all static and dynamic conditions that could exist, it becomes a staggering task for individuals charged with completions to perform the necessary mathematical calculations. The computer program permits advance calculations for several sets of conditions. INTRODUCTION In the Delaware basin of West Texas alone, 50 wells were contracted or drilled to 15,000 ft or deeper in 1965. Deep well activity is continuing in this and other areas on an expanding scale. Many of these deep wells require extensive stimulation for successful commercial production, and during these operations, pressures and temperatures are encountered that have a pronounced effect on the length of tubular goods. This length change during a large-volume, high-pressure stimulation treatment utilizing fluids considerably cooler than bottom-hole temperature can be of such a magnitude that permanent damage to casing and tubing will result unless mechanical design, pressures and fluid temperatures are evaluated and controlled. These pressure and temperature effects can be calculated. However, the process lends itself well to computer solutions because of the mathematical nature of the problem and the calculating hours involved in arriving at an answer. The engineering-hour demand becomes more severe as tapered strings are involved. On initial treatments on a given well, surface pressure and injection rate conditions are unknown, and offset well conditions have not proven to be a reliable method for making predictions. For these reasons, it has become rather standard procedure for operators to compensate for these uncertainties by placing unnecessary pressure and fluid temperature restrictions on stimulation design. On a number of occasions treating fluids have been preheated to as much as 160F as a means of compensating for thermal contmction resulting from pumping cool fluids. The maintenance of packer seals has been treated by Lubinski, Althouse and Logan',' and the problem of therma1 effects on pipe has been explored by Ramey." These works were expanded and the results made applicable to everyday oilfield terminology before submitting them to computer programming. The pressure and temperature effects on tubing movement previously mentioned occur simultaneously as fluid moves through the pipe. The pressure changes, for purposes of explanation, are categorized here as to the various effects these pressures have on a tubing string. These divisions are (1) the piston-like results of forces acting on horizontal surfaces exposed to pressure, (2) swelling or ballooning of the tubing along its entire length due to the forces of pressure acting against the tubing walls, (3) the elongation of tubing due to frictional drag and (4) corkscrewing of the pipe due to internal pressure. Thermal changes are also of great importance, as their results may be more significant than any of the pressure effects. Steel is an excellent conductor of heat and the earth is a relatively poor conductor. It has been calculated that pipe temperatures at depths of more than 20,000 ft approach within as little as 25" the temperfature of the surface fluid after pumping for 2 hours, or a drop in temperature in some treatments of more than 220F. The equations presented in this paper were developed for computer programming and simplicity of input information; therefore, numerical constants such as Young's modulus for steel (28 X 10\ si), the coefficient of thermal expansion of steel (6.9 X 10."IF) and Poisson's ratio for steel (0.3) are included with unit conversion factors. The moment of inertia of tubing cross-sectional area with respect to its diameter was changed to a constant times (D' — d') where D is outer diameter and d is inner diameter. Units in the equations are length in feet, diameter in inches, density in pounds per gallon, pressure in psi, rate in barrels per minute and time in hours. PISTON-LIKE REACTIONS A change in tubing internal dimensions and the exposure of other horizontal surfaces to different pressures on the inside and outside of the tubing result in a reaction much like a piston under pressure. Such is the case when the internal diameter changes in a combination string of pipe, when seals of a slick joint assembly are subject to pressure and in the end effects of a tubing string. The change in tubing length due to the piston effects of a slick joint packer is affected by the various diameters involved, the tubing pressure Ap,, the casing pressure ,Ap,, length of pipe L, densities of fluid in the tubing before and during pump-

By Voyle R. McFarland, Robert A. Burmeister, David A. Stevenson

The distribution of lead between phases in the Ag-Sb-Te system was studied using microautoradio -graphy. Two compositions were investigated, both containing an intermediate phase Known as silver antimony telluride as the major phase, and one containing AgzTe and the other SbzTes as the minor phase. For both compositions, two thermal treatments were used: nonequilibrium solidification from the melt and long equilibration anneals of the as-solidified structure. For each composition, lead was segregated in the minor phase of the as-solidified structure, but was distributed in the matrix after anneal. The electrical resistivity and carrier type were insensitive to the distribution of lead in the two-phase structure. ThERE has been considerable interest in the Ag-Sb-Te system because of its thermoelectric properties. The major interest has been in compositions on the vertical section between AgzTe and SbzTes, particularly the 50 mole pct SbzTes composition AgSbTez (compositions are conveniently expressed as mole percent SbzTes along the AgzTe-SbzTes section). One of the major problems in the proper evaluation and utilization of this material is the inability to control the electrical properties through impurity additions: all alloys prepared to date have been p-type, even with the addition of large amounts of impurities. It has been shown Wit all the compositions previously studied contain an intermediate phase of the NaCl st'ructure as a major phase (denoted by b) and a second phase, either AgzTe or SbzTe3, as a minor phase.'-3 One explanation for the unusual electrical behavior of this material is that the impurity additions have a higher solubility in the second phase than in the matrix; the impurity would segregate to the second phase, leaving the bulk matrix essentially free of impurity.4 In order to investigate this mechanism with a specific impurity element, the distribution of lead between the two phases was determined using autoradiography. Lead 210 was chosen because of the suitability of its 0.029 mev 0 particle for autoradiography and also because of the interest in lead as an impurity in this system.5'6 EXPERIMENTAL PROCEDURE Two compositions were taken from the vertical section between AgzTe and SbzTes, 50 mole pet SbzTes (Viz. AgSbTez) and 75 mole pct SbzTes, in which AgzTe and SbzTes appear, respectively, as the minor phase. Lead containing radioactive lead (pb210) was added to the above compositions to provide a concentration of 0.1 wt pct Pb. The material was placed in a graphite crucible in a quartz tube which was then evacuated and sealed. The samples were melted and solidified by cooling at a rate of 8°C per min and then removed and prepared for microa~toradiography. After autoradiographic examination of these samples, they were again encapsulated and annealed in an isothermal bath at 300°C for a number of days and prepared for examination. An alternate method of preparation employed a zone-melting furnace; the molten zone traversed the sample at a rate of 1.2 cm per hr and the solid was maintained at a temperature of 500°C both before and after solidification. This treatment had the same effect as solidification at a slow rate followed by an anneal for several hours at 500°C. In order to obtain the best resolution, thin sections of the alloy were prepared by hand lapping to a thickness of approximately 20 p. Other samples were prepared for examination by lapping a flat surface on the bulk sample. The resolution, although somewhat better in the former procedure, was adequate in both instances and the majority of the samples were treated in the latter fashion. A piece of autoradiographic film (Kodak Experimental SP 764 Autoradiographic Permeable Base Safety Stripping Film) was stripped from its backing, care being taken to avoid fogging due to static-electrical discharge. A small amount of water was placed on the sample, the film applied emulsion side down on the surface of the sample, and the sample and the film dipped into water in order to assure smooth contact. After drying, the film was exposed for 2 to 5 days, the period of time selected to give the best resolution. The film was developed on the specimen and fixed and washed in place. Two major factors must be considered in establishing the reliability of an autoradiograph: the in-

Jan 1, 1964

PLANS for development of the San Manuel ore- body have been worked out and are progressing parallel with construction of the surface plant. This property lies in the Old Hat mining district, Pinal County, Ariz., about a mile south of Tiger where the St. Anthony mine once produced gold, molybdenum, vanadidn, lead, and zinc. Two development shafts have been completed and serve as ingress for preparation of the 1475 haulage level and 1415 grizzly level. Three other shafts are being put down. The Nos. 3A and 3B shafts will provide the ore hoisting facilities. The No. 4 shaft, now being sunk, will be at the main mine service and supply yard, with primary function to provide the mine with supplies.

Jan 7, 1954

By Lombard Squires, W. K. Lewis, W. I. Thompson

Clays consist predominantly of hydrated silicates of alumina. The formula is frequently assumed to be A1203 . 2Si02 . 2H20,'and certain of I. North Carolina. Low plasticity. 11. Same as I, after washing. Low plasticity. III. Tennessee. Good plasticity. IV. Pennsylvania flint fireclay. Low plasticity. V. Laredo, Texas. Very plastic. CaO/Na2O corrected for GO2. VI. San Antonio, Texas. Fine grained, highly plastic. Moisture and CO2 were determined together at 18.8 per cent. VII. Selected crude bentonite, California. " Data from R. Ries: Clays. John Wiley & Sons, New York, 1927. them undoubtedly have substantially this composition, but in general the ratio of silica to alumina is considerably higher. However, they always contain water of chemical constitution, as shown by Table 1.

Jan 1, 1935

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,' it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:' log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0' systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick's first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula p = 2paR [1] where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homo¬geneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity pi and a lower layer, extend-ing to infinity, of resistivity p2. It has been shown by Lancaster-Jones2 that the apparent resistivity, obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the form pa/p1 = 1 + 4F [2] where Pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 - p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between Pa/P1, h/a and k. Such a set of curves for the case when pi > P2 is given in Fig. 1.

Jan 1, 1937