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By B. Mather

Discussion by B. Mather I was very glad to see an article on alkali-silica reactivity of concrete aggregate in Mining Engineering. It is a topic that should be reexamined every 45 or 50 years. The last paper (that I am aware of) that examined this topic in Mining Engineering was Rexford (1950), who, at the time, was chief of the Petrography Section, South Pacific Division Laboratory, Corps of Engineers, Los Angeles, CA. The paper was presented at the AIME meeting in Los Angeles in October 1948. Professor Leming's discussion generally reflects the current state-of-the-art; but it provides no references for more detailed information. I wrote a paper titled "How to avoid excessive expansion of concrete due to alkali-aggregate reaction," which was included in the Proceedings of the Second International Conference on Alkali-Aggregate Reactions in Hydroelectric Plants and Dams (Mather, 1995). In it, I emphasized that it was the hydroxide ion (not the alkali ion) that caused the pore fluid in the concrete to dissolve reactive silica, producing alkali-silica gel capable of taking up water, thereby, causing swelling and rupturing of the concrete. Excessive expansion will not occur unless there is a sufficient amount of potentially expansive alkali-silica reaction product and water. However, this will not occur unless there is a sufficient quantity of reactive aggregate and unless there is a mechanism by which the pH of the pore fluid can get well above the normal value of about 12.6. In many cases it is sufficient that the cementitious medium not only contains portland cement but also contains ground granulated blast-furnace slag (GGBFS) or a pozzolan such as fly ash, silica fume, metakaolin, volcanic glass or calcined shale - any of which may have been included for economic reasons. If, however, the person selecting the ingredients for concrete knows that the aggregate is reactive (with no alternate nonreactive aggregate available) and if the person knows that the only available portland cement has a high alkali content (i.e., more than 0.6% Na2Oe; Na2Oe = % Na2O + 0.658 x % K20), then it becomes irresponsible not to establish what reasonable precaution one should take. Professor Leming suggests using one of the following: 30% Class F fly ash, 50% GGBFS or 7% to 10% silica fume. My view is that one should prepare test specimens with the cement and aggregate to be used and then expose these both with and without at least two dosages of each of the various alternative materials (slag, pozzolan and lithium salts), so that the required dosage to control the expansion is established. Then, economic considerations can dictate the final selection. I would point out to the author that GGBFS is not a pozzolan and is not an admixture, but, rather, it is a latent hydraulic cement. An admixture is, by definition, a material other than hydraulic cement. I commend him for suggesting that aggregate producers should become more active in knowing about the reactivity of their products and the precautions needed to permit those products to be safely used in concrete. ? References Mather, B., 1995. "How to avoid excessive expansion of concrete due to alkali-aggregate reaction," Proceedings, Second International Conference on Alkali-Aggregate Reactions in Hydroelectric Plants and Dams, US Committee on Large Dams, Denver, CO, pp. 421-439. Rexford, E.P, 1950, "Some factors in the selection and testing of concrete aggregates for large structures," Mining Engineering, Trans. AIME, Vol. 187, pp. 395-402. Reply by M.L. Lerning Mr. Mather has once again provided a cogent and useful discussion. I am grateful to him for bringing these issues to my attention, as well as to the readers, and I am grateful for his discussion of several important factors in alkali-silica reactivity. Mr. Mather's discussion of the mechanism of alkali-silica reactivity (ASR) notes the critical role of the hydroxide ion. While the alkali hydroxides are highly soluble (reducing the solubility of the other primary hydroxide in pore solution, i.e., calcium hydroxide, and providing hydroxide ions that initiate alkali-silica reactivity), it is, as Mr. Mather quite correctly notes, the hydroxide ion that attacks the silica structure. This point was not clearly stated in my original article. As noted in the text, the requirements for mineral admixtures to mitigate or control ASR vary widely depending on the specific characteristics of the materials

Jan 1, 1998

By A. H. Geisler, F. Keller

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By F. Keller, A. H. Geisler

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By Ahmad Ghahremaninezhad, Noelene Ahern, Yeonuk Choi

Arsenic (As) is a toxic element and is a major contaminant in the extraction processes of some metals (e.g. gold and copper). Due to the toxicity of arsenic species, its removal from As-containing streams from extractive metallurgy processes and safe disposal is absolutely necessary. For nearly complete removal of waste arsenic species from metallurgical process streams, it is required to have arsenic in its pentavalent state (As5+ species). This study presents an oxidation process for arsenic species with air or oxygen gas as oxidant. Activated carbon (AC) or other carbon based materials are used to catalyse the oxidation reaction. Air or oxygen gas is the only consumed reagent which makes the economy of the process very attractive. The oxidation reaction can be carried out at ambient conditions (room temperature and atmospheric pressure) in less than 24 hours.

Jan 1, 2014

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By G. W. Doepel, W. P. Sibley

A three-dimensional, multilayer, mathematical model has been developed for predicting performance by mis-c.ible displacement. Areal and vertical coverage, total gas-oil ratio, propane-oil ratio and oil-recovery factor for the multilayer system are computed as functions of hydrocarbon pore volumes of solvent injected. The technique has been programed for use on the IBM-7090 digital computer and was used in calculating perfortnance for continuous miscible displacement of a five-spot, 50-layer .system. Results reported are based on the use of published laboratory data for a single, uniform five-spot layer. However, the technique is sufficiently generalized to calculate performance of any system of layers of any pattern configuration and mobility ratio, provided data are available to describe perfortilance of a single layer. The technique has also been adapted for predicting oil recovery resulting from various gas-driven slug sizes. The results presented for both continuous and slug-type injection show, that permeability variation has 0 significant effect on oil recovery but that solvent composition, within the range studied, has a lesser effect on oil recovery. INTRODUCTION Experience from many of the miscible-phase displacement projects currently in operation indicates that the injected solvent flows preferentially through the more permeable zones in the reservoir. This preferential solvent flow in the high-permeability streaks results in a reduction of vertical coverage (C,) and an attendant decrease in oil recovery. The multilayer technique presented in this paper uses areal coverage (C.,) data for a single layer from the literature and from laboratory measurements of displacement efficiency (herein referred to as microscopic coverage, C,,) to calculate areal coverage (C,) and vertical coverage (C,) for the multilayer system. Oil recovery for the multilayer system is obtained as the product of (Ca) (Cm) (Cv). It is assumed that C, in a single layer is 100 per cent; therefore, (C,) (Cm) is a measure of oil recovery from that layer. Data presented in the literature for a single layer generally deal only with areal coverage and/or microscopic coverage —but seldom specifically with oil recovery. Nevertheless, this technique is flexible in that either Ca and C,, of an individual layer or a direct measurement of oil recovery for the layer may be used. In developing this technique, the problem arose concerning a method of determining the relative amounts of solvent that will enter each layer during any increment of solvent injected. To solve the problem, a dimensionless equation was derived for expressing solvent injected into each layer as a fraction of total injection. A finite-difference method was applied in integrating the equation to determine oil recovery for the system of layers as a function of pore volumes injected. The technique subsequently was programed for solution on a digital computer. The method was applied to predict performance of a deep California reservoir under continuous miscible displacement and has been extended for calculating oil recovery as a function of slug size for gas-driven slug injection. The technique may be applied to any petroleum reservoir that can be adequately represented as a layered system, by considering permeability variation,1-3 permeability range and average permeability. Each layer is then assigned its appropriate permeability, porosity and hydrocarbon saturation. RESERVOIR VOLUME CONTACTED BY SOLVENT It has been recognized for some time that high microscopic coverage (C,) can be obtained by injecting a miscible agent, such as propane, into an oil reservoir. These high values of C,,, have been demonstrated in the laboratory and are normally between 80 and 100 per cent, depending on solvent and reservoir oil composition as well as on reservoir temperature and pressure. In miscible-phase displacement, because there is no interface between solvent and oil, effective permeability to solvent is the same as that to oil. (This assumes that oil saturation has not changed and that water is immobile.) Consequently, mobility ratio (M) simply reduces to that of viscosity ratio . Perrine4 and Habermann5 have shown that large

By Jr. Allan

"Although the advantages of large-capacity air receivers for underground mines are plainly evident from published information about various installations in the United States and abroad, details of their construction are not generally known in this country., Ordinary present-day air-compressor installations servicing mining machines are designed to supply air at a specified pressure in sufficient quantity to meet the peak demand of the mine,2/ although this demand may exist for only a few minutes out of 24 hours and, as usually happens, eventually exceeds the capacity of the compressor. Most of the receivers provided with these compressors (to a certain degree of standardi¬zation) are capable of storing a volume of air approximately equal to that compressed in 1 minute by the machine.3, 4/ As a result, during peak-load periods the compressor operates at full load capacity without maintaining kick-off pressure. At other periods of the work cycle, production of compressed air is intermittent.At least one large mine5/ has adopted large-capacity receivers to reduce wear on its air-compressing system caused by the sudden demand of peak loads. Under the old system, the compressors jumped suddenly from half speed to full speed; boilers furnishing steam to the compressors were taxed heavily to provide the increased requirements of power; and machines using the air, among which were four large hoists, were required to operate at 65 pounds per square inch rather than at the 90 pounds per square inch for which the compressors were regulated. Operation of air machines, especially drills, at pressures lower than those for which they were designed decreases their efficiency and increases maintenance costs. In addition, air that comes directly from the compressors has had little opportunity to cool and dry enroute.6./ As a result, quantities of compressor lubricant and water are carried into the machines that use the air. When expansion occurs in the cylinder or turbine of such engines, the temperature of the air drops, and this oil and water is precipitated. The water washes away lubricating oils in the machine, causing poor performance and high cost of maintenance; the compressor oil, in addition to being a poor lubricant for compresed-air engines, exerts a corrosive action on gaskets and rubber hoses.7/Reduction of peak demands on air compressors by large receivers lowers power costs by establishing more nearly constant load factors,8/ and in some cases by permitting the use of smaller compressor capacity.8,9/Load factor is the ratio of average demand to maximum demand; a low load factor costs money.10/Elimination of high-peak demands raises the load factor by making the average and the maximum demand more nearly equal. Further savings may be made possible by large receivers where their use permits charging to be done at night in regions having lower power rates during that period.11/Where ordinary receivers are used, compressor breakdowns cause immediate work stoppages in the mine owing to lack of air. Similarly, the capacity of a large receiver has been known to permit uninterrupted work in the mine until the compressors have been returned to service.9/Large-capacity receivers, either steel-tank or underground rock-chamber, offer a practical solution of many existing problems by providing a sufficient reserve of compressed air within the pressure range required for efficient operation of machines to level off peak demands on the compressor. The com¬pressors operate when the demand has reduced the pressure in the receiver below the regulating pressure and until all air used from the receiver has been replaced. It has been found possible in at least two mines,8.9/ one of which the author has visited, to entirely eliminate one compressor and to obtain more efficient performance from the remaining one by the construction of an underground coal-chamber receiver.8/"

Jan 1, 1950

By W. C. Knopf, I. M. LeBaron

In the Carlsbad area potash is dry-mined and wet-concentrated. Wet concentration involves recircu-lation of saturated brines, with resultant difficulties of brine disposal and inherent losses in recovery through solution of the KCl. A dry beneficiation process for potash minerals would offer many advantages over present methods. International Minerals & Chemical Corp. has been working on development of a dry process for some time. This article is a progress report. Potash ores available in this country are largely mixtures of halite and sylvite contaminated with slimes and often with many sulfate and magnesium minerals. Electrostatic concentration of KCl when the contaminating minerals are in low percentage has been accomplished. Continuous production of better than 60 pct K2O concentrate from high potassium sulfate ores has not been demonstrated at the present time. Laboratory Procedure: Laboratory work on electrostatic beneficiation of potash minerals has been carried out using both pure crystals and mined ore. Electrostatic separation of the two main components of potash ore, sylvite (KCl) and halite (NaCl), is accomplished by first heat-treating the ore to allow for electric charging of the particles. Preferential exchange of' electrical charges between different mineral particles through surface contact is the principal mechanism involved. After proper conditioning of the particle surfaces, the oppositely charged minerals are dropped vertically into a horizontal electric field having a field gradient from about 5000 to 15,000 v per in. The particles are free-falling in the field. A suitable power supply is used to produce the proper total voltage for the electric field. Total required voltage is, of course, a function of electrode spacing. A typical electrode arrangement with power supply is shown in Fig. 1. In general, the total voltage on any system is 75,000 to 90,000 v. Power consumption is negligible, as leakage at insulators and corona discharge are the main losses in the system. Optimum preheat temperatures for pure material components generally are not the same as for mined minerals. Fig. 2 shows clearly that maximum recovery on a 50 pct pure KCl, 50 pct pure NaCl mixture occurs at a preheat temperature of about 600°F. In this test the preheat mixture was allowed to cool to about 225°F before dropping through the electric field. The optimum temperature for sep- aration is practically never the optimum temperature of preheat. Optimum separation for mined Carlsbad potash ores occurs when a preheat temperature closer to 900°F is used, as shown by Fig. 3, which plots percent sylvite (KCl) in the concentrate and tails as a function of preheat temperatures. Here again the ore was allowed to cool to about 225°F before separation. It should be noted that efficiency of separation increases continuously with increasing preheat temperatures until incipient fusion of the ore takes place at about 950°F. The increase in optimum preheat temperature for Carlsbad ores over the pure minerals can be traced to the effect of the clay slimes intimately associated with the mined potash. If the slimes associated with the ore are removed by washing with alcohol or other non-aqueous material, the necessity of preheating to the high temperature is removed. This temperature range has been proved critical within these limits during continuous pilot plant operation. Concentrate and tailings grade and optimum recovery also are functions of the temperature of the potash mineral particles during separation in the electric field. Fig. 4 presents data indicating that feed to the rougher pass should range between 150°F and 275°F for best results. It has been found by subsequent pilot plant work that these temperatures can be maintained in actual operation.

Jan 1, 1959

By John P. Hager, Igor A. Wilkomirsky

The thermodynamic properties of the Pb-Ag system have been determined between 775° and 950°C by the cell: Electrotransport measurements on silica-saturated PbO-SiO2 melts established that the conduction was entirely ionic and that lead is present only in the divalent state. The activities of lead and silver exhibit Positive deviations from ideal behavior. In dilute solutions the activities of lead and silver follow Henry's law. The values obtained for yhb and yig at 1200°K are 1.49 and 1.69, respectively. Determination of a portion of the liquidus curve agrees well with the established phase diagram. provides an accurate means for the thermodynamic study of liquid alloy systems. However, Wagner and wernerl have shown that cells of type I are limited to alloy systems for which the reaction at the alloy-electrolyte interface will be extremely small. The traditional electrolyte for cells of type I has been a low melting point mixture of group IA chlorides, to which a small amount of the compound ACIZa has been added. However, the choice of a chloride electrolyte may not always be practical, in that the Gibbs free energies of formation of the compounds ACIZ, and BCIZb may not be sufficiently different to minimize Reaction [I]. On the other hand, the Gibbs free energies of formation of the oxides of metals A and B may be sufficiently different to minimize Reaction [I]. In this case, the use of molten oxide electrolyte would be clearly advantageous. In the present study, the thermodynamic properties of the Pb-Ag system have been investigated using the cell: Previous galvanic cell studies on the Pb-Ag system2'= are not reliable due to the displacement reaction between the alloys and the chloride electrolyte. Wagner and ~erner,' using Laitinen and Liu's' value at 450°C for the standard electrode potential of Reaction 111, have estimated the percent error in the activity of lead bPb) when using a chloride electrolyte. At 1000°C the error for xpb = 0.10 is 12 pct. Taking the Gibbs free energies of formation for PbClz and Ag cI,' and the equations of Wagner and Werner,' the error in apb at 1000°C and Xpb =0.10 was calculated to be 140 pct. However, using the Gibbs free energies of formation for Pb O' and an estimated value for Ag 20, the error in apb when using a molten oxide electrolyte at 1000°C was estimated to be less than 1 pct for The virtual reaction of cell I1 for the passage of n Faradays of positive electricity from left to right in the cell is: where 5 is the Faraday equivalent (23,063 cal per v equivalent), E is the electromotive force of the cell in volts, and n is the number of Faradays of electricity required for the transfer of 1 g-atom of lead through the cell. The value of n should be equal to 2 since lead is generally divalent in oxide melts. However, the presence of either tetravalent lead ions or electronic conductivity through the molten oxide electrolyte will result in a value of n greater than 2. Bockris, Kitchener, and Davies' have determined the amount of ionic conductance in a liquid PbO-SiO2 mixture (xPbO= 0.50) at 920°C by measurement of the volumes of CO and C& evolved at a carbon anode during electrolysis. From their data a value of 2.13 * 0.16 was calculated for n. Although their measurements indicate the possible presence of multivalent lead ions and/or electronic conductivity, their measurements were not at silica saturation and no definite conclusions can be drawn. However, as a result of the electrotransport measurements described in the next section the ;due of n can be taken as equal to 2.

Jan 1, 1969

By M. C. Flemings, R. Mehrabian, G. E. Nereo

Analytic expressions were developed and applied in two preuious papers to predict effects of solidification variables on macrosegvegation. In this paper, experiments are reported to test the analyses quantitatively and qualitatively. Good quantitative agreement is obtained between predicted and measured compositions for the following types of segregation (all experiments were on laboratory-size ingots of Al-4.5 pct Cu alloy): (a) inuerse segregation, (b) composition distribution in ingots solidified with unidirectional heat and fluid flow, (c) simulated centerline segregation, and (d) segregation resulting fro, change in solidification cross section. In addition, qualitative agreement of prediction of theory with experiment is obtained for (a) segregation resulting from sudden change in heat extraction during solidification, (b) centerline segregation in a bidirectionally solidified ingot, and (c) under-riser positive segregation. IN two previous papers,''2 it was shown that a variety of apparently different types of macrosegregation result from the same basic mechanism. This mechanism is the flow of solute -rich liquid to feed solidification and thermal contractions. Analytic expressions were derived and examples given of their application to predict macrosegregation. Calculations were for Al-4.5 pct Cu alloy. In this paper, we describe a series of experiments designed to test results of the foregoing calculations. All experiments were on laboratory-size ingots (weighing 10 lb or less), of A1-4.5 pct Cu alloy, nominal composition. APPARATUS AND PROCEDURE A typical mold and chilling arrangement used for unidirectional solidification is shown in Fig. 1. Before casting, this assembly was placed in an electrically heated air furnace, and heated to 680" to 700°C. When the plaster reached the desired temperature (usually 1 to 2 hr after the furnace temperature), the mold was filled through a funnel extending from the outside of the furnace into the cavity. The assembly, with liquid, was held for several minutes to allow convection to subside. The coolant, either air or water (depending on the desired solidification rate), was turned on and the ingot solidified. With the four sides and top insulated, heat removal for solidification was through the bottom surface, resulting in a fully columnar structure. Design of the casting cavity was varied, as discussed below, to produce desired macrosegregation effects. However, for castings solidified with unidirectional heat flow, the top was always open to the furnace atmosphere and temperature. The bottom sur- face rested on a chill through which the heat was extracted, and all other surfaces were insulated with plaster. In one case to be discussed, the mold design was changed to obtain bidirectional solidification. In this case, two vertical chills were used (on two faces of the mold) and the bottom was insulated. In a last case discussed, that dealing with under-riser segregation, experiments were conducted in bottom-chilled sand molds at ambient temperature. Except for this one case, all experiments were conducted in the electrically heated air furnace as described above. In many ingots, thermocouples were used to obtain continuous records of solidification. In all cases, these were chromel-alumel couples with output continuously monitored on a twelve-channel recorder. Where thermocouples were employed, these were embedded in the refractory mold walls during mold-making so their heads extended to the vertical centerline. Six to nine couples were employed, placed at intervals from the chill. METAL-MEL TING PROCEDURE Aim analysis was A1-4.5 pct Cu; alloy was prepared from high-purity aluminum (99.9 pct Al) and A1-Cu master alloy (50 pctOFHC Copper, 50 pct high-purity Al). The A1-4.5 pct Cu alloy was cast in 5- to 7-lb ingots for subsequent remelting for the macrosegregation experiments. Melting for ingot casting was as follows. After preheating the melting crucible for an hour or more, the charge was melted and superheated to a temperature of 690" to 720°C. After stirring, the melt was degassed with chlorine for 10 min. After stirring again for 1 min, a gas sample, under reduced pressure, was taken. When the sample was gas-free, the crucible

Jan 1, 1969

By E. G. Woods, A. G. Comer

A mathematical model is presented and solved for determinution of the saturation distribution and pressure in a radial gas-storage reservoir. The model consists basically of two parts: (I) the growing gas-bubble core, and (2) the surrounding aquifer. Since the total pressure at the injection well is a function of the two-phase flow in the gas bubble and the unsteady single-phase flow in the aquifer, the resistance to flow in both zones was taken into consideration. The assumptions involved for both the radial equivalent of the Buckley-Leverett two-phase-flow equation and the injection-pressure equation are as follows: (I) the geometry is radial, (2) the gas bubble is free to expand or contract, (3) compression or expansion of the gas within the bubble may occur at the beginning of a time step, (4) the fluids are immiscible, (5) water is incompressible within the gas-storage region whereas it is compressible outside of this region, (6) a stable gas-water interface exists and (7) gas injection occurs at a constant rate or a series of constant rates. The mathematical model was solved numerically using an IBM 650 computer. A comparison is presented between the predicted results of the model, the results assuming steady-state flow and the actual initial injection-pressure history of an operating reservoir. Using the initial field pressure for a basis, the average deviation between the predicted pressure and the actual field pressure was less than 4.3 per cent. INTRODUCTION Underground storage of natural gas in abandoned oil fields, in abandoned coal mines, in caverns and in aquifers has had varying degrees of success. The lack of these first three facilities in the vicinity of most major gas marketing areas is leading more and more to storage in virgin aquifers. For the most part, this storage in aquifers has led to the study upon which this paper is based. Several excellent papers have been published discussing the problems involved in the underground storage of natural gas; however, to these writers' knowledge, none of them considered the two-phase flow of fluids in the gas bubble and the fact that the gas bubble will grow or shrink in size depending upon the injection and withdrawal history of the reservoir. Not only will both of these factors influence the required injection pressure, but also they will have a definite bearing upon the amount of water production occurring upon withdrawal from the storage area. To solve this problem on an IBM 650 computer, several simplifying assumptions were made. Only the drainage portion of the relative-permeability curve was considered, thereby neglecting any hysteresis effects introduced during an imbibition cycle. The quantity of gas withdrawn during the period of the field study was only a small percentage of the total gas in place; therefore, this assumption is justified. For the problem studied in this case, the combined effects of capillarity and gravity were assumed to be negligible. This assumption becomes less valid as the formation thickness or the average pore diameter increases markedly. The justification of these assumptions should be studied in each case. THEORY This mathematical model for the prediction of saturation distribution and pressure for a radial gas-storage aquifer is based upon the equations for radial two-phase fluid flow'.' and for radial, unsteady-state, single-phase fluid flow.' The two-phase flow is considered to take place in a "core" whose radius is equal to the maximum radius that the gas zone will attain, as indicated in Fig. 1. The injection-withdrawal history is approximated by a series of constant flow rates. Within the "core", gas is assumed to behave as a semi-compressible fluid; that is, the gas is assumed to have a constant density based on the average gas-zone pressure for the flow period. Between each constant-rate time increment, the gas density is allowed to change. This involves an iterative solution of the pressure equation. The liquid phase in this zone is considered to be incompressible, whereas it behaves as a compressible liquid outside of this region. The equations of incompressible flow in the "core" may be written for the gas phase

By Paul Nicholas, Raju Gottumukkala

"India’s economy is expanding with rapid urbanization. Improvement in infrastructure is a keystone to the Indian government’s economic plans, including expansion of transit systems. Most of these systems are designed with elevated and underground sections. New Delhi, a city of 23 million people, suffers from heavy traffic congestion and pollution. The transit (metro) system is seen to be of critical importance. Phase 3 of the Delhi transit system project is 140 kilometers (km), with 40 km of twin-bore tunnels requiring 35 tunnel boring machines (TBMs) for construction. Transit systems are also under design or construction in Chennai, Bangalore, Kolkata, Hyderabad, Jaipur and Mumbai. Most have twin-bore tunnels. At present, 55 TBMs are operating on underground metro construction, and future projects will increase this number. This paper highlights the unique challenges of construction of underground metro systems in highly congested urban environments, using Kolkata and Delhi systems as examples. INTRODUCTION The first transit system in India was constructed in Kolkata (India’s third-largest city by population.) This line is 28 kilometers (km) in length, has underground and at-grade sections, was built in phases, runs north/south, and has 24 stations. This project was sanctioned in 1972, started construction in 1984, and was completed in 1995. The tunnels were constructed primarily by cut and cover methods with some open-face, compressed air shield tunneling. In 2006, the urban transport policy recommended construction of transit rail systems in all urban cities with a population exceeding 2 million. Further, in 2014 the central government stated that it would assist in financing transit systems in all cities with a population of over 1 million. In 2015, the central government approved the development of transit systems in 50 additional cities across India with a budget of $75 billion (see Figure 1). Transit development is just part of a huge expansion in planned rapid transport systems, which include metro, bus, high-speed rail, and monorail systems. Metro systems will include elevated and underground sections with twin-bore tunnels and underground stations. In the Delhi/National Capital Region (NCR), now the largest city in India by population, Delhi Metro Rail Corp (DMRC) was formed in 1995 as a joint venture company between the central government and Delhi state. DMRC operates the Delhi metro system. (see the case studies described later in this paper). DMRC has developed an external function to carry out studies and to offer consultancy to other cities planning transits. Since its inception, DMRC has produced Detailed Project Reports (DPRs) for every metro and monorail project in India. In 2012, DMRC became a partner in the management consultancy for Jakarta Mass Rapid Transit System, its first project overseas. DMRC became a model organization for other cities to follow. These cities have included Chennai, Hyderabad, Kolkata, Bangalore, Jaipur, Mumbai, Ahmedabad, and Nagpur. Other cities (e.g., Lucknow and Patna) are in the metro planning phase. Metro systems are under construction or partially operating in Hyderabad, Bangalore, and Jaipur."

Jan 1, 2016

By Hertha Freche

THE diffusion of magnesium and silicon from the core into the high-purity coating of Alclad sheet is important commercially, and led to the use of a duplex product for the study of diffusion by means of spectro-graphic analysis of successive layers. It has been found that in the duplex materials the diffusion of magne-sium from an undersaturated aluminum-magnesium alloy into its high-purity aluminum coating is approximately of the same order of magnitude as the diffusion of silicon from a saturated aluminum-silicon alloy into its high-purity aluminum coating. However, if magnesium and silicon are both present in the alloy in the ratio of Mg2Si they appear to diffuse in the approximate ratio of this compound. Finally, if the alloy contains silicon in excess of the amount required by magnesium silicide, the amount of diffused silicon in the high-purity aluminum coating will also be in excess. The interdiffusion of metals in the solid state is of both scientific and technical interest, because it is helpful in the study of the alloy structure and in the solution of problems pertaining to the strength and surface condition of the fabricated product. W. C. Roberts-Austen1 carried out the first quantitative determination of the coefficient of diffusion of gold into lead. This classical experiment was followed by a series of investigations on the diffusion of metals and nonmetals in iron and steel and in nonferrous metals and alloys. Recently the diffusion of copper in coated strong aluminum alloys was investigated by A. Burkhardt2. This appeared to be the first published investigation on the diffusion of metals into aluminum.

Jan 1, 1936

By G. S. Hume

Activity in geological exploration and drilling continued in Canada in 1945 at about the same rate as in the previous year, but with disappointing results as far as new production is .concerned. Both in the foothills and on the Plains of Alberta, however, there are wildcat wells that have either given encouraging shows or some production, which are very important in relation to future developments. The normal decline of Turner Valley, the largest producing field in Canada, has continued, and this decrease has not been offset by new discoveries. In addition, the closing of the Canol pipe line on March 31, 1945, isolated the Norman Wells field in the Mackenzie River valley, and the outlet at present. is confined to supplying the relatively small local requirements. This

Jan 1, 1946

By J. O. Marsden

Part I in this series of papers considered the chemistry of medium-temperature pressure leaching of copper sulfide concentrates and reviewed the metallurgical testing and initial process development for this technology. This initial work resulted in the development of a process flowsheet utilizing superfine grinding (to a P98 of 12 to 15 µm and P80 of 6 to 7 µm), pressure leaching at 160° to 170ºC, followed by conventional solution extraction (SX) and electrowinning (EW) for the recovery of copper. However, this process required a significant amount of concentrated acid to be fed to the pressure leach vessel to meet the reaction requirements, representing a cost of between $0.03 and 0.05/lb copper (2006 basis) produced by the process. It was immediately recognized that the development of a process that did not require such a large acid addition would be advantageous. This paper, which is Part II in the series, describes the development of a process that incorporates medium-temperature pressure leaching and direct electrowinning (DEW) in a novel and innovative process flowsheet. Phelps Dodge (a subsidiary of Freeport-McMoRan Copper & Gold Inc.) refers to this as the ?MT-DEW-SX? process. Part III in this series covers the large-scale demonstration of the MT-DEW-SX process at Bagdad, Arizona; and Part IV addresses the development and design of a full-scale commercial application at Morenci, Arizona.

Jan 1, 2007

By E. C. Reed

Drilling activity in Nebraska during 1945 continued to decline slightly over that of the previous year. Eight tests for oil and gas were completed during the year, of which seven were wildcats and resulted in dry holes. The eighth test, an inside location in the Dawson field of Richardson County, yielded an initial production of about 3o bbl. per day with 86 per cent water from the Hunton formation. Five wells were drilling at the end of the year, two of which were wildcats. Two of the drilling wells were deepening operations in the Dawson and Falls City fields and the third was an inside location in the Falls City field, which appears likely to result in a producer. Most of the operations were in Richardson County but two wells were drilled in Dawes and Gage Counties and one each was drilling in Holt and Washington Counties at the end of the year. There were no new discoveries of oil or gas.

Jan 1, 1946

By E. Yan, M. Mankosa, E. B. Wasmund

Mechanical cells are the dominant unit operation in base metal rougher flotation applications worldwide. As economic demand for metals increase, and as the feasible ore grades decrease, the installed capacity of mechanical flotation units worldwide has greatly increased, adding significant capital and operating cost. One opportunity to improve this situation is to use fundamental knowledge to make the industrial flotation process more efficient. A key insight is that the flotation process can be optimized by dividing the processing of the pulp into two distinct fluidic environments; a collection cell where air and pulp mix in a highly energetic compartment, and a low energy gravity separation cell. This is the basis of the “2-stage flotation device” that has been patented by Eriez and marketed under the tradename StackCell™. Two industrial case studies will be presented to highlight the potential metallurgical and commercial advantages of the StackCell. In the first, a train consisting of three pilot scale StackCells (each 0.6 metre diameter) was run in parallel with a train of conventional mechanical cells in a major copper concentrator and benchmarked against a batch Denver test. In the second, the performance of a 3 metre diameter StackCell in a nickel sulfide cleaning application was benchmarked against a batch Denver test. The flotation kinetics observed in the StackCells were 2.4 to 2.9 times faster when compared with the lab Denver test. In the first case study, the kinetics of the StackCell was about six times faster than conventional mechanical cells. It is hypothesized that the efficiency improvement in kinetics is because of reduced “drop-back” during the froth recovery phase, which is reduced because of the reduction in the shear that is present in a conventional mechanical tank cell. This result suggests that a 2-stage flotation system can be used to reduce the working volume of flotation units by five to six times. This would allow operators to significantly reduce the size of their flotation lines for a comparable flotation objective. Some discussion will follow about the scale-up criteria, maintenance and operability issues, comparisons of layout, and possible cost savings. INTRODUCTION The solution that most equipment suppliers have offered to reduce the cost of mechanical flotation equipment over the last 30 years has been to increase the size of the flotation unit cell (Mankosa, 2017). For example, three 100 m3 machines with three smaller motors, mechanisms and control valves could be replaced with a geometrically similar 300 m3 with a larger version of each ancillary component. While there are some efficiencies and cost improvements to be gained by this approach, it does not take advantage of fundamental insights into the flotation process, and it does not represent a step-change in terms of process design or economic benefit for the customer. The advantage of the “bigger is better” approach is that there is past experience of incremental improvements by making cells larger and there is a well-established scale-up method, which allows practitioners to estimate equipment capital costs based on very simple laboratory test- work. A different paradigm, which is gaining interest rapidly is to use a unit operation in which it is easier to optimize the flotation process, which will be described in this paper. This approach is often referred to “2- stage flotation”. Because this approach is new, it is important to benchmark it against existing conventional technology and to demonstrate a robust methodology for sizing equipment and flowsheets. This paper aims to address these issues with two case studies.

Jan 1, 2019

By William R. Barton

Iron and steel slag represent man's most successful attempt to date to profitably utilize a solid waste. Its consumption represents a solution to a solid waste problem and also represents tonnage of natural aggregates that will not have to be mined with concomitant disturbance of the land. Slag has been produced as long as iron has been made; but until a little more than 50 years ago, it was mostly a waste product to be disposed of with as little effort and cost as possible. Huge piles of waste slag were generated over the years of iron and steelmaking. Sporadic use was found for small amounts starting with slag (from Catalan forges) used for road bases by the Roman Empire. The first recorded sustained commercial use was, as is often the case in man's history, for making war. Some profit- conscious munitions maker in the 16th century realized that he could make cannon balls of slag instead of the more precious iron. Other small-volume uses gradually developed: cast building blocks, slag-lime mortars and cements, slag wool, ballast, road base, and, finally, in concrete. But it was not until after World War II that the true potential of blast-furnace slag as a construction aggregate was really recognized. Now nearly all blast-furnace slag produced is used, and much of the earlier stock- piles in the U. S. have been reduced or entirely consumed. Steel slag for aggregate use has been in commerce for only the past 10 years, and use has increased rapidly (10-50% per year) during the past 5 years as blast-furnace slag supplies became depleted. However, much remains to be accomplished in determining character and optimum conditions of use for various types of steel slags before such slags will realize their full use potential. Although slag represents only 2% of construction aggregate materials used in the U.S., its production involves certain features that make its production record far more important than national tonnage figures would indicate. Its source is in iron and steel production and concomitantly slag availability is restricted to those areas where iron or steel is produced. In such areas, it often represents one of the principal aggregates marketed and, because of special properties that make slag a selected aggregate for certain uses, the tonnage imbalance may be overcome by the importance of its contribution to quality or special characteristics of end products. The location and number (Fig. 1) of slag plants handling this annual production is governed by the geographic makeup of the iron producing industry. Prior to the period marked by World War 11, most blast furnaces were in the Great Lakes area-Pittsburgh, Cleveland, Chicago, Gary, Buffalo, Detroit, Youngstown, and Toledo, with exceptions at Baltimore, Bethlehem, and Birmingham. Since that time, iron and steel facilities have been established in Texas, Utah, and California. Today 85 slag plants in 15 states provide employment for almost 2000 persons. The slag plants also recover almost 4 million tons of slag-encrusted iron each year for return to the blast furnaces. Much of the success in developing uses for slag can be attributed to the efforts of the National Slag Association founded in 1918. Since then, it has conducted numerous field and laboratory investigations to demonstrate the properties and uses for slag and slag products. These investigations have resulted in total recognition of blast-furnace slag as a construction material of consequence. The American Society for Testing & Materials Designation C125 recognizes blast-furnace slag as "the nonmetallic product consisting essentially of silicates and aluminosilicates of

Jan 1, 1975

By D. D. Smith, D. P. Squier, E. L. Dougherty

A system of differential equations describing the temperature behavior of fluid injected at constant surface temperature in a well is derived and .solved analytically. A formula for the fluid temperature at any time and depth is given, as well us a special formula valid for very large times. These formulas are used to calculate temperatures for several typical cases. The results indicate that, initially, the temperature of the water entering the formation is considerably lower than the injection temperature. This condition lasts for only a short period— less than three days for most cases of practical interest. Following this highly transient period, during which the temperature of the fluid entering the formation builds up to about 50 to 75 per cent of the injection temperature. the system enters a quasi-steady state in which the temperature changes are very slow. After severl years, the bottom-hole temperature will still be 50" to 100°F lower than the injection temperature, hilt the heat losses may he tolerable. INTRODUCTION Predicting the behavior of a hot-water flood requires that the temperature of the water entering the injection interval be estimated. This report describes the development and solution of a system of equations which describes the temperature behavior of the injected water in the wellbore with certain simplifying assumptions. The only previous means known to the authors for describing such a process is that of Moss and White.' Their results appear to be close to those obtained by our method in the practical cases which were compared; this agreement is largely due to the fact that in our method temperature soon approaches a quasi-steady state, as was assumed in their method throughout. However, our model covers all times, is continuous (whereas the Moss-White model depends on breaking the depth into discrete intervals) and. we feel. more closely describes the physical problem. FORMULATION OF THE PROBLEM PHYSICAL SYSTEM AND ASSUMPTIONS The injection procedure consists of pumping water at a fixed surface temperature T., down an infinitely long cylindrical well or tubing of inner radius Any material exterior to the water column such as mud, casing, or cement is regarded as part of the formation. The general behavior of the system may be described qualitatively as follows. When the hot water is first introduced into the system, the temperature difference between the formation and the water is large, resulting in a high rate of heat transfer. As a result, the temperature adjacent to the wellbore rises very quickly. Because the segment of the formation adjacent to the wellbore largely controls the heat transfer rate, the heat transfer rate will become relatively constant when this portion has reached a temperature close to that of the water opposite it. The temperature of the water and formation then increase very slowly with time. The length of the initial highly transient period and the temperature of the water at its conclusion will be functions of depth, injection rate, injection-string radius, surface injection temperature and the physical properties associated with the water-formation system. The following additional assumptions were made. 1. There is no heat transfer by radiation in the system. 2. There is no heat transfer by conduction in the vertical direction in either the injection stream or the formation. 3. The linear volumetric and mass flow rate of the water is constant throughout the injection stream. 4. No horizontal temperature gradient exists in the injection stream. 5. The product of density and heat capacity is constant for both the water and the formation, and the formation thermal conductivity is constant. 6. Initially, both the water in the wellbore and the reservoir are at a temperature given by the (constant) ambient surface temperature plus the product of depth and geothermal gradient (assumed constant). At large distances for the wellbore (r m), the formation will remain at this temperature. 7. The water temperature and the formation temperature at r — r,, are equal for all depths D. DERIVATION OF EQUATIONS The differential equation satisfied by the fluid temperature T,(D, t), which is obtained by writing a heat balance on a cylindrical differential of volume dV of the injection string between the depths D and D i dD, is

By H. Dykstra

Calculated wellbore pressures were obtained for parameters of radilcs ratio and permeability. In all cases bur two, after-production was allowed to occur for one day. The calculated pressure build-up data were compared with actual pressure build-up data from a condensate well. The paper discusses the comparison, gives reasons for, inability to match calculated (2nd actual data, and presents conc1usions derived from the comparison. INTRODUCTION Considerable information has been published on the decline in wellbore pressure for oil and gas fields resulting from production of fluids. Considerable information also has been published on pressure build-up for oil fields, but relatively little has been published for gas and condensate fields. Perrine' summarized the equations derived for pressure build-up in oil wells and showed how the different methods could be applied. On the other hand, very little theoretical information has been published on pressure build-up in gas or gas-condensate wells.2-4 Tracy,' by pointing out the similarity between the equation describing oil wellbore pressure decline and the equation describing gas wellbore pressure decline, showed how methods of pressure build-up analysis could be applied to a gas well. In analyzing pressure build-up data for gas or gas-condensate wells, it would be very desirable to compare actual pressure build-up data with calculated pressure build-up data. Such a comparison would lead to a better feeling for the quantitative picture of gas-well build-up curves and would help to establish a degree of confidence in a given build-up curve. This paper discusses the comparison and presents conclusions made from it. Calculated wellbore pressures are given for parameters of radius ratio and permeability. In all cases but two, after-production was allowed to occur for one day. The work was done in an attempt to evaluate the reserves of a gas-condensate field. As will be discussed later, it was not possible to make an evaluation. METHOD OF CALCULATION The method used for solving the depletion and pressure build-up behavior for a gas-condensate well was that developed by West, Garvin and Sheldon.5 or the IBM 704 computer program used, it was assumed that liquid condensing out of solution would have only a minor effect on the flow behavior. Therefore, the field was treated as having single-phase flow, with the gas saturation S, remaining constant at unity minus the connate-water saturation Sw. As will be discussed later, this may not have been a good assumption. It also was assumed that oil production could be considered as equivalent gas production by using a conversion factor based on an analysis of the liquid produced. An outer boundary condition of no-flow was assumed. BASIC DATA The data required for the study were reservoir properties, fluid properties and production data. Reservoir properties included the following: thickness h, 179 ft; porosity, 0.194; connate-water saturation, 0.43; gas saturation, 0.57; permeabilities k, 1.0, 0.5, 0.25 and 0.15 md; radius ratios re/rw, 800, 1,000 and 2,000; wellbore radius rw, 5 in.; initial reservoir pressure P, 6,529 psia; and reservoir temperature, 272°F. The selection of permeabilities was based on core-analysis data showing an average air permeability of about 2 md. With a relatively high connate-water saturation, the average effective gas permeability would be about one-half, or less, of the air permeability. The selection of radius ratios was based partly on the observed rapid decline in wellbore pressure during production and partly on the fact that the well was believed to be located in a relatively small fault block. Reservoir fluid properties were obtained from a reservoir fluid study on a recombined sample of gas and condensate. Gas formation-volume factors were calculated from pressure-volume measurements made at reservoir temperature. Gas viscosities were calculated by the method of Carr, et al,G from an analysis of the re-combined sample. These data are shown as a function of pressure in Table 1. The production schedule from the gas-condensate