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By Harold B. Janzen, M. A. Nobles

Campbell and Martin1 described a new exploratory logging tool which was developed as the result of a new concept of the phenomenon that takes place when a porous formation containing mobile hydrocarbons and irreducible interstitial water is invaded by mud filtrate. They postulate that invasion will create a bank of interstitial water between the flushed zone and the undisturbed formation. This postulate was confirmed by Wyllie.' Thus, if R,, is greater than R, and mobile hydrocarbons are present, the resistivity profile with increasing radii from the borehole is high:low:high, as shown in Fig. 1. If mobile hydrocarbons are absent, the bank of interstitial water is indistinguishable from the undisturbed formation and the resistivity profile, when R is greater than R,, is high:low, as shown in Fig. 2. The zone containing the bank of interstitial water and residual oil was named the "low zone". Campbell and Martin conducted extensive electrolytic wedge and resistivity analog model studies to select a logging system that would reflect the presence or absence of the low zone. The system they selected was that of a family of lateral curves. The model studies indicated that the presence of a low zone could be detected in approximately 60 to 70 per cent of the producing sand reservoirs with a family of lateral curves provided that the sonde effectively occupies 90 per cent of the diameter of the hole. These studies were conducted with D, = 5d. The presence or absence of the low zone is best determined by a plot of the apparent resistivity vs spacing as shown in Figs. 3 and 4. A dip or inflection in the profile that repeats at successive depth intervals is considered diagnostic. To reduce the shunting effect of the hole and mud, a sonde of insulating material that is surrounded by a series of flexible rubber bumpers was designed. The bumper efficiency is considered to be the ratio of the bumper diameter to the hole diameter. Field tests conducted by Campbell and Martin on 10 wells with a tool that provided for station readings indicated that dips or inflections could be detected in 19 out of 25 known producing zones. INSTRUMENT DEVELOPMENT Halliburton developed a logging system to simultaneously and continuously record eight lateral curves. The instrumentation is described in the literature.' The original logs made

By J. L. Huitt, B. B. McGlothlin, D. K. Lowe

Published correlations for the principal aspects of hydraulic fracturing were combined into a digital computer program to facilitate the study of interrelated variables. The computer program includes individual relationships for fracture width during pumping, fracture area generated, propping agent embedment, flow capacities of propped fractures and transport of propping agents in horizontal fractures. The effects of more than 20 treatment and formation parameters on the predicted results of hydraulic fracturing treatments were studied. The effects of these parameters were determined for (I) fracture width during injection, (2) fracture width after the overburden comes to rest on the propping agents, assumed not to be crushed, (3) generated and propped fracture area, (4) location and concentration of propping agents in the fracture when injection ceases, (5) flow capacities of the various propped sections of the fracture and (6) expected increase in the well productivity. The effects of propping agent, formation and fracturing fluid parameters on well productivity are discussed. The parameters that were found to have the most pronounced effects on hydraulic fracturing treat~nents are injection rate, treatment volume, fracturing fluid coefficient, size and amount of propping agent, spearhead volume, well drainage radius and formation capacity. INTRODUCTION Many correlations have been published for predicting effects of various parameters that are considered in the design of hydraulic fracturing treatments. The Carter equation' can be used to predict generated fracture radius as a function of fracture width, fracturing fluid leakoff and other parameters. Fracture width can be determined by use of the Perkins and Kern correlation' in which the fracture width is related to the fracture radius, fluid injection rate and certain formation and fracturing fluid parameters. Wahl and Lowe et aL4 have reported methods of predicting the location of propping agents in fractures when pumping ceases. The former study is applicable to the case where the ratio of propping agent diameter to fracture width is less than 0.1. The latter is applicable when this ratio is greater than 0.1. These studies showed that the propping agent placement in horizontal-radial fractures depends principally on how the individual particles are transported in the fracture by the carrying fluid. Particle transport in fractures is determined by local fluid velocity in the fracture, fluid and particle properties, and the size of the particle relative to the fracture width. The distribution of propping agents, effective overburden pressure and formation rock strength control the propped fracture width6 by controlling the extent to which the propping agent particles embed into the fracture faces. From the distribution of propping agents and the propped fracture width, fracture flow capacities can be calculated or the various regions of the fracture. The flow capacities and the radial extent of these regions can be combined with reservoir information to predict the productivity increases for fractured wells. In all these studies, the effects of certain treatment and/ or reservoir parameters on one facet of fracturing can be predicted only if other facets which the parameters affect are fixed. For instance, fracture width and radius are interrelated; that is, to calculate the value of one, the value of the other must be known. Also, some parameters influence more than one aspect of fracturing. For example, prop-pant transport is a function of both fracture width and fluid viscosity. but fracture width is itself a function of fluid viscosity. Since these calculations are complex and the parameters interrelated, it is not possible to write an equation with which the over-all effects of treatment parameters can be solved explicitly. For these reasons, the correlations for determining the effects of the parameters which are most significant in hydraulic fracturing treatments have been incorporated into a digital computer program. COMPUTER PROGRAM The program, which was written for an IBM 7094 computer, can be used to predict results of most of the combinations and values for the treatment parameters that are ordinarily considered for fracturing treatments. A spearhead of fracturing fluid and a propping agent-carrying fluid with different fluid properties can be taken into account. Also, the total volumes and relative amounts of the spearhead and carrying fluids can be varied. Two different propping agents (as used in tail-in operations) and a wide range of formation properties and injection rates are considered. The computer program (Fig. 12) consists of several sets of calculations. First, the final flooded fracture radius and average fracture width at the cessation of pumping are calculated. This is done by simultaneous solution of the Perkins and Kern fracture width equation and the Carter equation for flooded fracture radius (equations used in the computer program appear in the Appendix). The next step is to determine local fluid velocity in the fracture as a function of time and radius. Since it is not possible to write this function in closed form expression, a table of velocity values is generated by the program and stored for subsequent use. The time span from the beginning of

By P. Pietrokowsky

RECENTLY a comprehensive investigation of the various sigma binary alloys was published by Duwez and Baen.1 It was shown that the following conditions are necessary for the formation of the sigma phase: (1) the difference in atomic diameters of the two alloying metals must not be more than about 8 pct; (2) of the two elements which form sigma, one must exhibit a body-centered cubic structure while the second metal must be face-centered cubic, at least in one of its allotropic forms. In addition, a tetragonal unit cell was proposed and powder patterns of six sigma phases were indexed for d spacings greater than 1.640 kx. Since the indexing, based on tetragonal symmetry, led to only fair agreement, the possibility of sigma being orthorhombic was investigated. Various methods for indexing orthorhombic powder patterns are de- scribed in the literature.' The method used in this investigation was a graphical examination of the differences in values of sin' 9 for the adjacent lines of the powder diffraction pattern. This method led to a complete indexing of the Cr-Co (60-40) pattern. Because of the strong similarity between the various sigma alloys, it was then possible to assign indexes to the patterns of Fe-Cr (50-50), Fe-Cr-Mo (30-30-40), Fe-V (50-50), Co-V (50-50), and Ni-V (50-50). The values of sin' 9 and indexes of the six sigma alloys, together with visually estimated intensities, are presented in table 1. In general, the similitude between the six patterns is quite good. For spacings greater than 1.75 kx a few differences are noticeable. In the Ni-V pattern, no (320) exists and the two strong lines (030) and (031) are separated by only two lines of lower intensity, unlike any of the other sigma patterns. However, very little is known about the Ni-V phase diagram and it is possible that the equal atomic percentage composition in this system lies in a two-phase region. At lower spacings there is a close analogy between the patterns. The planes

Jan 1, 1951

By D. Mizer, J. B. Clark

In a recent investigation of the entire magnesium-yttrium phase diagram, Gibson and Carlsonl report the maximum solid solubility of yttrium in magnesium as 8.0 wt pct Y at 1050°F (565°C). However, independent studies of the precipitation in magnesium-yttrium alloys, 2 conducted prior to the publication of the above phase diagram, indicated a greater solid solubility of yttrium in magnesium. Accordingly, the magnesium-rich region of the diagram was re-investigated to determine more accurately the liqui-dus, solidus, and solvus of the magnesium solid solution in this system. Metallography and thermal analysis were chosen as the best corroboratory methods for accurately determining this region of the diagram. A magnesium-yttrium master alloy was prepared from yttrium of 99.9 pct purity and singly sublimed magnesium of 99.9 pct purity. Subsequently, the twelve magnesium-yttrium alloys shown in Fig. 1 were prepared using standard alloying procedures for magnesium. Metallographic samples of the alloys were heat treated under an SO, atmosphere in an electric furnace capable of control within ±3oF of the desired temperature. Alloy samples for the metallographic determination of the solvus, and for the precipitation studies were solution treated at 1000° F for 16 hr. Subsequent aging times for the solvus determination varied from a minimum of 6 hr for the higher temperatures up to 816 hr for lower temperatures. Periods of 30 min at temperature were used to generate liquation for the metallographic placement of the solidus and eutectic horizontal. The liquidus and the eutectic horizontal were determined by thermal analysis. Simple time-temper- ature heating and cooling curves were obtained from 10-g alloy samples heated and cooled in a well-insulated electric furnace. An Iron-Constantan thermocouple was placed in direct contact with the sample. The thermocouple did not contaminate the alloy sample since metallographic examination showed that the alloy melt did not wet or attack the thermocouple. The heating and cooling rates were approximately 5 to 8OF per min. The standard metallographic procedures for magnesium were used in polishing and etching the magnesium-yttrium alloys studied. Glycol etchant* was etchant was used to reveal precipitate in the solvus determination. The redetermined magnesium-rich region of the magnesium-yttrium diagram is shown in Fig. 1. The

Jan 1, 1962

By J. F. Shirley, H. K. Burke

In January, 1964, three years of laboratory and pilot plant test work reached its culmination. The San Manuel Div. of the Magma Copper Co. switched its molybdenite extraction circuit from the sodium hypochlorite-ferrocyanide process to the new process described in this paper. The San Manuel Div. Concentrator of the Magma Copper Co. is located near San Manuel, Ariz., approximately 45 miles northeast of Tucson. The concentrator treats approximately 35,000 tons of ore per day containing about 0.85% copper and 0.025% molybdenite. The San Manuel ore body is a disseminated copper deposit in quartz monzonite and quartz monzonite porphyry. The primary copper mineral is chalcopyrite; minor amounts of chalcocite, bornite and covellite are also present in varying degrees. Pyrite makes up somewhat more than half the sulfide content of the rock. The molybdenite is nearly always found on fracture faces or associated with quartz veinlets.' On January 9, 1964, the sodium hypochlorite-ferrocyanide process that had been used for molybdenite recovery was replaced by the following process: 1) A conditioning step with hydrogen peroxide, sulfuric acid, sodium cyanide and zinc sulfate. 2) A two stage rougher flotation step with stove oil and sodium ferrocyanide. 3) One cleaning step with sodium ferrocyanide. 4) One cleaning step with sodium hypochlorite and potassium ferricyanide. 5) Four cleaning steps with an anti-foam Exfoam 636 and potassium ferricyanide. COPPER CONCENTRATOR Since molybdenite recovery is closely allied with previous steps in the operation, the copper concentrator will be briefly described first. The ore is ground to approximately 5% plus 65-mesh and 65% minus 200-mesh in a two-step grinding circuit consisting of rod mills in open circuit and ball mills in closed circuit with rake classifiers. A straight forward rougher circuit producing only one concentrate is used. The rougher concentrate is combined with the discharge from the regrind ball mills and is then cycloned, with the overflow going directly to the cleaner circuit and the underflow going to the regrind mills. The feed to the cleaner circuit is approximately 90% to 94% minus 325 mesh. The cleaner circuit consists of two stages in which the tailing from the final cleaner stage is returned to the primary cleaner and the primary cleaner tailing is returned to the rod mill discharge at the head of the circuit. Approximately 0.013 lb of the allyl ester of amyl xanthate (S-3302) per ton of ore is added to the rod mills and approximately 0.006 lb of sodium isopropyl xanthate (2-11) per ton of ore is stage added down the rougher banks. The frother used is methyl iso-butyl carbinol (MIBC) and it is added at various points in the grinding and the rougher flotation circuits. Lime is added to the ball mills and/or to the rod mills to maintain the desired pH in the rougher flotation. The rougher flotation has been operated at various pH levels between 10.5 and 11.5. Fuel oil is added in the regrind mills at a loading of approximately 0.01 lb per ton of ore. Factors Which Directly Affect Molybdenite Recovery: It has been found at San Manuel that, to obtain maximum molybdenite recovery, an oily type flotation collector must be added in the grinding circuit. When molybdenite is crystallized in the characteristic platy form, which appears to be the case almost all of the time at San Manuel, its surface has a greater tendency to adhere to oils than water. 2 Of the several oily type collectors available on the market, the allyl ester of amyl xanthate seems to be the best molybdenite promoter. The floatability of San Manuel's molybdenite does not appear to be affected, at least up to a pH of 11.5, by lime. It has been reported that at several plant operations high lime alkaline circuits have adversely affected the molybdenite recovery.3,4 It has been found through microscopic studies that the bulk of the chalcopyrite will float before the molybdenite in both the rougher and cleaner circuits. It is necessary to add fuel oil to the regrind mills to enhance the

Jan 1, 1965

By J. S. Levine

A series of four displacement experiments has been run in a large alundum core. Flow potential distribution in each liquid phase was measured continuously through oil-wet and water-wet capillary barriers, using a null-point pressure balance, and saturated distribution was determined from electrical resistivity measurements. A method has been devised for calculating the effective (and relative) permeability to each phase at any time and at any point in the flow system for the transient displacement process. Relative permeability points have been calculated and average curves drawn for oil displacing water and water displacing oil. The values of dynamic capillary pressure have also been determined. Data have been substituted into the generalized Buckley-Leverett fractional flow equation and a comparison between actual and theoretical breakthrough recoveries is shown. Displacement experiments have been performed in the laboratory for many years in an effort to determine the effect of a number of parameters on multiphase flow in porous materials. In the literature of petroleum technology, Wyckoff and Botset' were among the first to develop the relative permeability concept and to show experimentally that oil, gas, and water can flow simultaneously through a porous medium in a precise way governed by certain fluid properties, by the relative saturation of each fluid, and by characteristics of the medium itself. Somewhat later, Leverett2 and Hassler, Brunner, and Deahl11 developed some theoretical concepts of capillary behavior in porous materials. The work of Buckley and Leverett3 presented a theoretical analysis of immiscible liquid displacement based on the equation of continuity and the Darcy equation for viscous flow of each fluid. Subsequent investigators attempting to verify the Buckley-Leverett equation have, in general, deliberately neglected the capillary pressure term or have performed experiments in such a manner that it could be neglected. Terwilliger, et al4 in 1951, obtained agreement between theory and experiment for the constant rate displacement of water by gas in a long vertical sand column. Rapoport and Leas5 have investigated the

Jan 1, 1955

By Thomas T., Read

ALTHOUGH the first colonists in the area that is now the A United States, whether Spanish, French or English in nationality, were usually keenly interested in the possibilities of mineral wealth, it is a curious and interesting fact that none of them happened upon the mineral deposits that eventually were to make this the greatest mineral-producing country; up to 1800 it would probably have been rated as rather poor in minerals. Spanish explorers traversed the southeastern United States with- , out finding the Appalachian gold deposits that aroused so much interest in the early nineteenth century; Coronado sought in vain for the seven golden cities of Cibola; and the important gold \ deposits of California were not discovered until the political sovereignty of the region had passed from Mexico, which had held it for three centuries. The French also held Canada for nearly two centuries (and the British for another century) without finding the mineral deposits in Ontario and Quebec that now are so important. Though they knew of the copper of the Keweenaw peninsula, the lead ores. of Wisconsin and Missouri, and the coal of Illinois in the seventeenth century, these deposits were all too remote for exploitation. In the area held by Great Britain, iron smelting was planned at Jamestown as early as 1619 and was actually begun at Lynn, Mass., in 1643. The industry grew slowly, at first, but had reached considerable importance before the Revolution. Commercial bituminous coal mining began about 1750 in Virginia but anthracite mining in Pennsylvania was not started until 1800. As a result there was naturally little interest in the technical aspects of mineral prodnction here before 1800 by any except the few people who were actually engaged in it. Students of natural science were much interested in minerals, however. The activities of those who rank as geologists are so thoroughly covered in

Jan 1, 1941

By C. E. Birchenall, H. M. Schadel, G. Derge

EXISTING distribution data' for silicon between liquid iron and silver at steelmaking temperatures, 1500" to 1600°C, has made activity relationships in liquid silver-silicon alloys desirable as a method of determining the silicon activity in molten iron. To this end, through the use of radioactive Ag110 and the molecular beam technique described in a previous paper,' the vapor pressure of silver as a function of temperature has been measured over three silver-silicon alloys containing 3.9, 9.3, and 15.4 atomic pct (eutectic composition) silicon. The technique was that described for pure silver with the exception that a porcelain liner was used inside

Jan 1, 1951

By AIME AIME

THE report of the united. States Steel Corporation for the' year 1928 gives the, following ,figures of raw materials and' finished products . Raw materials, tons :

Jan 1, 1929

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

By William Hume-Rothery

MR. CHAIRMAN, LADIES AND GENTLEMEN: I need not say how much I appreciate the honor of being asked to lecture to you, and how much I would thank you for your kind invitation. It is encouraging to feel that the abnormal restrictions of the war have been relaxed sufficiently to allow a free exchange of scientists between our two countries, and I hope that some of you will be persuaded to go to England, and to visit us at Oxford, so that I may repay a little of the kindness I have received from you. As this is one of the first lectures since the end of the war, I have thought it well to describe some of the advances in the theory of alloys which were made in the years between the two World Wars. From the point of view of theoretical science, these years have been of outstanding interest in the history of metallurgy. They have been years in which the development of new and more accurate experimental methods has led to the revelation of many new facts. At the same time, the theoretical developments have enabled some of these facts to be viewed as parts of a general scheme, and we may say that some of the foundations of metallurgical science have been laid. This work was naturally stopped by the Second World War, and it can therefore be reviewed as one definite stage in the development of our Science. To illustrate the new advances, I shall deal mainly with the alloys of copper and silver, since these have revealed many of the general principles. SOLID SOLUTION At the beginning of our period, the first steps in X-ray crystal analysis had been taken, and copper had been found to crystallize in the face-centered cubic structure (Fig I). The determination of this structure naturally was of immense importance in the understanding of our subject, because it meant that we were at last in a position to appreciate the underlying structure out of which the crystal of copper was built. The earlier science of metallography had shown that in many alloys of copper the addition of a second metal in not too large proportions resulted in the formation of a homogeneous alloy which was regarded as a solid solution of the one metal in copper. Fig 2, for example, shows the so-called equilibrium diagram of the copper-zinc alloys, and here you will see that there is a solid solution of zinc in copper extending to something of the order 35 to 40 at. pct zinc.

Jan 1, 1947

By Thomas V. Falkie, Robert Stefanko

Recently The Wall Street Journal featured a series of articles titled "The Dirty Work-Brutal, Mindless Labor Remains a Daily Reality for Millions in The US.-Mining Coal, Shoveling Slag, Gutting Hogs Pays Bills But Can Drain Spirit, Hope." The article was devoted to describing how tough and dangerous is mining (and some other jobs) and how rough life is for miners and their families. Similarly during the past few years some psychiatrists and sociologists have devoted increased attention to the attitudes and life styles of miners. Unfortunately most of their approaches have been neither scientific nor objective, and very little good clinical research has been done on the subject.

Jan 1, 1971

By W. M. Morris

THE volumetric behavior of isobutane at temperatures below its critical temperature has been studied by several investigators. Seibert and Burrell1 measured the vapor pressure of isobutane from the ice point to the critical temperature. Dana and co-workers2 determined among other thermodynamic quantities the density of the saturated liquid and the saturated gas and the vapor pressure from approximately 0° to 130° F. Sage and Lacey3 studied a number of the thermodynamic properties of this hydrocarbon from 70° to 250° F. The specific volume in the gas and liquid region was determined at pressures up to 3000 lb. per sq. in. ? throughout this temperature interval. In addition, the vapor pressures were measured at 30° intervals. These data taken together serve to establish the thermodynamic behavior of isobutane at temperatures between 0° and 250° F. with reasonable accuracy. However, apparently there are no data available at the higher temperatures. For this reason an investigation of the volumetric behavior of isobutane at temperatures between 100° and 460° F. was carried out with apparatus that has been described in another paper (A.I.M.E. Tech. Pub. 1127).

Jan 1, 1939

By Robert Mehl

IT is generally understood by workers in the field of the crystal struce ture of metallic alloys that terminal solid solutions are of two types, the substitutional and the interstitial. In reviewing the literature, the work of Weiss1 on the crystal structure of the alpha copper-tin alloys wa-encountered, in which a new type of terminal solid solution was proposed. In brief, Weiss' findings showed that the density of the alloys calculated from the side of the unit face-centered cube on the assumption of simple substitution-that is, with four atoms to the unit face-centered cell-was much higher than the density measured directly. It was suggested that the assumption of four atoms to the unit cube is not valid for these alloys, and that each unit cube contained less than four atoms; in other words, that one tin atom replaces more than one copper atom, leaving some atomic positions unoccupied. Such a structure, if verified, would have far-reaching significance in the study of the crystal structure of metallic alloys. It would indicate a complexity in terminal solid solutions not hitherto suspected and might encourage work leading to the discovery of other alloys of the same type, and perhaps to types intermediate between it and the two recognized types. It is of importance, therefore, to reinvestigate these alloys with respect to the type of solid-solution structure obtaining therein.

Jan 1, 1929

By Arthur Hockman, Howard W. Jaffe, Howard F. Carl

THE problem of establishing practical techniques for evaluating natural corundum ores arose from the desire to improve the existing purchase specifications for crystal corundum procured by the Federal Government for stockpiling. Such purchase specifications had been developed for a large number of products, including minerals and ores considered to be critical and strategic because of the country's dependence on foreign sources of supply. It will be apparent to anyone considering the subject of purchase specifications that the determination of whether or not a submittal meets the specifications is a prime consideration. Consequently satisfactory specifications for minerals should not only incorporate physical, chemical, and mineralogical requirements that are practical but should also establish the means by which both buyer and seller can be assured that materials meet stated requirements.

Jan 4, 1954

Melbourne, capital of sedate Victoria, is oddly enough the home of a game known as "Australian Rules." Euphemistically described by devotees of the game as a cross between Rugby and Soccer, it appears to the novice to be more akin to organized mayhem. They don't even play it in some parts of Australia, but in Melbourne 60,000 to 80,000 whooping spectators throng the Cricket club of a Saturday afternoon to see a match. Actually, the game is fast and grueling but the victory laurels always go to the skillful team, the one that plays the ball rather than the man. Australians also play the ball in their ground rules affecting those interested in mineral exploration and mining. Prospecting Rights: Throughout the island continent, nearly all mineral rights are reserved to the Crown, administered by the individual states and, in the case of the territories by the Commonwealth government. The owner of the surface rights cannot sit on his minerals, and the term minerals even includes sand and gravel. Prospectors are protected by mining codes or ordinances of the various governments, which are quite similar from state to state.

Jan 10, 1964

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute. Since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1° to 2°C. per min. with or without slow stirring (Fig. 1). By this method the lead-rich end of the lead-antimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the' liquidus curve of the .binary alloys did not intersect at the eutectic temperature. An equivalent effect was observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent investigation by Pellini and Rhines,1 who determined the eutectic temperature to be 251.5°C. The observation that the curves of primary crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomenon by assuming the existence of a compound Sb4Pb. He felt that super-cooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3. the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature of 250° to 252°C. at a rate of cooling of about 6°C. per min. Abel, Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous, publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic contains only 11,4 to 11.5 per cent antimony. (Previous analyses by Stead4 in 1881 gave 13 per cent:) Weaver," however, reported in 1935 that cooling curves indi-

Jan 1, 1943

By N. H. Jensen

SINCE the sixties, Utah has been one of the leading metal mining states of the Union. During the last fifteen years its mines have supported the largest smelting center in the world. Its rank as a metal producing state is reflected by its 1924 production which had a value in excess of $65,000,000 making it the leading silver producing state, third in both copper and lead and sixth in gold production. During the past year, metallurgical developments for the recovery of zinc contained in lead ores has made rapid progress so that the future zinc output will be of substantial importance. The largest silver mines of the nation and the world's largest open cut copper mine are within its borders. Settlement of Utah started in 1847, with the advent of the "Mormons," and originally the area of the state was much greater than now. The first metal mining

Jan 1, 1925

By John P. Goheen

Considerable work has been done in developing a pyrometer to measure the temperature of molten brasses, bronzes, and aluminum in the crucible. On account of the high melting points and the amount of zinc and sulfurous fumes given off from molten brasses, the conditions are somewhat severe for a thermocouple of standard design; but satisfactory results are obtained with a portable pyrometer, 3 ft. (0.9 m.) of connecting lead wire, and a special 5-ft. nickel-nickel chromium thermocouple, composed of rods 1/4in. (6.35 mm.) in diameter. The lower 12 or 24 in., as desired, may be made detachable so that new tips may be connected at little trouble or expense. The portable instrument need not be of the extreme high-resistance type, as the movable parts of the galvanometer of a lower resistance instrument may be better constxucted to withstand the continuous handling such an instrument receives. Platinum-platinum rhodium thermocouples, protected with porcelain and graphite tubes, have been used, but the lag in registering the temperature is too great. It has been found that the range of temperature for various brasses is as follows: Red brasses...............2200-2250" F. (1205-1234" C.) Yellow brasses............2250-2400" F. (1234-1318' C.) Bronzes..................2300-2550" F. (1260-1400" C.) A recent test with a portable pyrometer having a range of 2600" F. with a bare 1/4 in. heavy exposed couple 5 it. long and a handle attached at the upper end showed that the temperatures of molten aluminum under varying conditions in an oil-fired crucible furnace and one of the Simplex type were as follows: CRUCIBLE, OIL-FIRED FURNACE SIMPLEX FURNACE Temperature of metal in furnace....... 1540" F. (837" C.) 1530" F. (834" C.) Temperature in ladle after skimming at furnace......................... 1480" F. (805" C.) 1440" F. (784" C.) Temperature in ladle after skimming at floor near mold................... 1440" F. (784" C.) 1430' F. (778" C.)

Jan 1, 1923