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By V. de Ruiter

In the northwestern part of the Netherlands lies the deepest solution salt mine in the world. The company operating the mine is Frisia Zout bv (part of the K+S group). Extracting the NaCl from caverns at a depth of nearly 3000 m has a lot of challenges. Continuously monitoring, among others, the flows, pressures and salt concentrations is necessary to safely and economically mine the salt. A system has been set up at Frisia to be able to monitor the data from a distance. Data has been put in graphs to monitor the trends daily. All gauges are also continuously monitored to maintain accuracy. With this system a better understanding of the mining process has been made and has led to many optimizations.

Jan 1, 2008

The Engineers Society of Western Pennsylvania, William Penn Hotel, Pittsburgh, Pa. K. F. Treschow, Secretary Since 1880 this society has been publishing Proceedings containing papers on a wide variety of engineering and related subjects The Proceedings are issued monthly throughout the year (except for the months of August and September each year) and the monthly Proceedings from February of one year to and including January of the next are also collected in volumes The latest is vol 47, for 1931 The rate of subscription for the monthly Proceedings is $5 per year throughout the Postal Union, single copies (monthly), 50 cents each The price of the yearly volumes from vol 17 to date is $5 each, unbound. The Secretary will quote prices for

Jan 1, 1933

By K. R. Vost

"In situ" measurements of the surface heat transfer coefficient in underground airways by K. R. VeST,* B.Se. (Glas.), M.Se. (N.S.W.) (Visitor) Few "in situ" measurements have been made of the surface heat transfer coefficient in mine airways despite the importance of this coefficient in determining the heat flow into the ventilating air. In this paper, the values obtained at various air velocities and the comparisons of these values with theoretical values are given. Examples are also given ofthe errors which would result if rock surface temperatures were obtained by extrapolation from temperatures further into the rock without taking into account the time delay which occurs before a given change in air temperature reaches the points from which extrapolation is carried out.

By C. Allen, A. Roy, J. W. Evans

A spouted bed electrode (SBE) has been used, in laboratory experiments, to electrowin zinc from zinc chloride electrolytes with the objective of determining the suitability of this electrode for commercial application. Zinc was successfully electrowon at current densities ranging up to 4,38 lA/m2, which are an order of magnitude larger than those used at present in the zinc industry. Current efficiencies, for the cell with the SBE, have been as high as 90% and DC energy consumption as low as 2.8 kWh/kg zinc deposited. The performance of the cell has been measured as a function of current density, anode type, cell diaphragm, addition of tributyl ammonium chloride and purging of the electrolyte (to remove dissolved chlorine).

Jan 1, 2000

By J. Hanna, H. R. Gonzalez

Four Ca-bentonitic clays from Alabama were evaluated for use in diammonium phosphate (DAP) or urea ammonium nitrate (UAN) fertilizer suspensions. The viscosity and gel strength of suspensions prepared with different proportions of a Western bentonite clay and sodium-exchanged Alabama clays were measured as a function of clay content and dispersant concentration. The results obtained suggested that three of the Alabama Ca-bentonites would replace about 40% of the more expensive Western bentonite in UAN and DAP fertilizer suspensions. The performance of the Nu-modified clays, prepared according to the Tennessee Valley Authority soda ash method, was as good or even better than those observed for the Mg-, NaIMg- or K-modified clays. The TVA clay modification procedure appears to be reliable and cost effective.

Jan 1, 1991

By A. Haque

The shear behaviour of infilled joints produced from ordinary gypsum plaster (gyprock) and bentonite was investigated in the laboratory under Constant Normal Stiffness (CNS) conditions. Shear tests were performed on saw-tooth profiles having Joint Roughness Coefficients (JRC) of 4.75 and 9.25 under an initial normal stress (sno) of 0.30 to 1.10 MPa, and at a normal stiffness (kn) of 8.5 kN/mm. Test data under the same sno and infill thickness to asperity height ratio (t/a) were analysed for two different sets of JRC. The peak shear stress plotted against the t/a ratio under constant sno revealed an increase in peak shear stress with the increase in JRC, up to a t/a ratio of about unity. The effect of roughness on the peak shear stress was observed to be minimal when the t/a ratio exceeded 1.40. A mathematical model for the prediction of peak shear stress due to the increased infill thickness has been developed based on a hyperbolic stress-strain relationship and energy balance principles. The model predictions are in good agreement with the laboratory observations. Le comportement de cisaillement des joints remplis produits à partir de plâtre ordinaire et de bentonite a été étudié dans le laboratoire sous des conditions de rigidité normales constantes. Des essais de cisaillement ont été réalisés sur des profils en dents de scie ayant des coefficients de rugosité des joints (CRJ) variant de 4,75 à 9,25 sous un effort normal initial (sno) de 0,30 à 1,10 MPa, et une rigidité normale (kn) de 8,5 kN/mm. Le résultat des essais conduits sous la même contrainte et épaisseur de remplissage au rapport aspérité/hauteur (t/a) ont été analysés pour deux ensembles différents de CRJ. La variation de l'effort de cisaillement maximal contre le rapport t/a sous une contrainte normale constante a indiqué une augmentation de l'effort de cisaillement maximal avec l'augmentation du CRJ, jusqu'à un rapport de t/a proche de l'unité. L'effet de la rugosité sur l'effort de cisaillement maximal a été minimal quand le rapport t/a a excédé 1,40. Un modèle mathématique pour la prévision de l'effort de cisaillement maximal dû à l'épaisseur accrue du remplissage des joints a été développé sur la base de la variation entre contraintes hyperboliques et déformation et sur des principes de bilan énergétique. Les prévisions du modèle sont en bon accord avec les observations de laboratoire. Das Scherverhalten in mit gewöhnlichem Gips und Bentonit gefüllten Klüften wurde im Labor unter Bedingungen konstanter Normalsteifheit (CNS) untersucht. Scherversuche wurden durchgefürt für Sägezahnprofile mit Werten des Fugenrauhigkeitskoeffizienten (JRC) von 4.75 und 9.25 unter Normalspannungs-werten (sno) von 0.30 bis 1.10 MPa, und bei Normalsteifheit (kn) von 8.5 kN/mm. Testresultate für gleiche Werte von sno und Verhältnis Fülldicke zu Rauhigkeit (t/a) wurden untersucht für zwei verschiedene Werte von JRC. Die Beziehung zwischen maximaler Schubspannung und und t/a Verhältnis unter konstantem sno zeigte einen Anstieg der maximalen Schubspannung mit zunehmendem JRC, bis zu einem t/a Verhältnis von etwa 1.0. Der Einfluss der Rauhigkeit auf den Maximalwert der Schubspannung war minimal solange das t/a Verhältnis den Wert von 1.40 überstieg. Ein mathematisches Modell wurde entwickelt für die Vorhersage der Schubspannung die von zusätzlicher Fülldicke erwartet werden kann, ausgehend von einer hyperbolischen Spannungs-Dehnung Beziehung und dem Energiegleichgewichts-prinzip. Die Modellvorhersagen zeigten gute Uebereinstimmung mit den Laborbeobachtungen.

Jan 1, 2003

By H. J. Hutson

BRS, Inc. has utilized Carlson's Natural RegradeTM software to design the reclamation and stabilization of abandoned open pit uranium mine spoils, AML Project 16N, located in the Gas Hills Uranium District in central Wyoming. This work was completed for the State of Wyoming's Abandoned Mine Land Program (AML) on preSMCRA (Surface Mining Reclamation and Control Act) sites for which no reclamation obligation existed. The project successfully stabilized an eroding spoil dump, enhanced the local view shed, created habitat diversity and provided a significant source of fill material for open pit highwall hazard mitigation efforts. Additionally, the project served to evaluate innovative reclamation design methods, engineering software and grade control technology. This project was nominated for a National Association of Abandoned Mine Land Programs award by the State of Wyoming. The results of this project will be presented as a case history of the Natural RegradeTM approach to surface mine reclamation. Based on the successful application of this new mine reclamation technology on the AML 16N Project, reclamation designs for spoils associated with planned underground uranium mine operations at the Velvet Mine in the Lisbon Valley Uranium District of Utah for Uranium One USA, Inc have been prepared and will be presented. Critical elements will be the encapsulation of unsuitable materials, long term hydrologic stability, and sequencing and staging of ore and mine waste for final reclamation surface construction. The goal of the Uranium One Velvet Project will be to apply best available technology to reclamation planning and fully integrate the reclamation design with the mine planning. Benefits of the approach should include improved public and regulatory perception of the project, facilitate mine permit approvals and the eventual timely release of reclamation bonds, as it is anticipated the stable landform created through this process will result in more rapid stabilization of the site to pre-mine geomorphic conditions. NATURAL REGRADETM CASE STUDY AML Project 16N, D-9 and K Pit Reclamation Project, is located in an intensely disturbed area of the West Gas Hills Uranium Mining District in Fremont County, Wyoming. The overall design calls for the placement of approximately 7 million cubic yards of backfill materials in the D9 and K Pits, imported from adjacent mine spoils including the Central Spoils, and from local highwall excavation. Figure 1 shows the location of the Central Spoils excavation area, as well as the D9 and K Pits fill area. The entire project is located on public lands administered by the Bureau of Land Management, Lander, Wyoming District Office. No access controls are in place at the abandoned mine sites. The public lands are administered under a multiple use land policy including grazing of range land, public recreation, active mining and exploration, and oil and gas. The project site is located along Fremont County Road No. 5, which is a moderately well traveled road. Reclamation of the numerous and large abandoned open pits in the Gas Hills Uranium District has reduced the risk of death or injury to the public. Site History and Background The Gas Hills Uranium District was mined by multiple companies during the period from 1955 to 1981. The uranium was hosted in the Wind River formation, a sequence of soft sedimentary layers of interbedded sandstone, clayey shales, and conglomerates. Uranium was precipitated out of ground water in classic roll front deposits, which are found from very near surface to depths greater than 400 feet. Prior to the enactment of the Surface Mining Control and Reclamation Act of 1977 (SMCRA), very little reclamation work was performed when mines were abandoned or closed. The State of Wyoming Abandoned Mine Lands Program has worked to mitigate hazards associated with large open pits, control migration of unsuitable materials and restore watershed functionality of lands in the district. Additional reclamation is being performed by mining companies on bonded lands. Figure 2, Gas Hills Uranium District aerial photograph, shows the extent of the mining disturbance in the district. [ ] Project Hazards and Concerns The purpose of AML Project 16N is to mitigate hazardous conditions and risk to the public associated with open pit highwalls and toxic, acid forming, and /or radioactive mine waste materials. The D9 and K Pits are contiguous open pits characterized by an 8,800 foot long hazardous highwall that averages over 200 feet tall. In addition to the physical hazard presented by the highwall, the project addresses

Jan 1, 2009

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

By Rex O. McLellan

The formation of a monovacancy in a metal is simulated in an elastic model by the displacement of the surface of a small spherical cavity in a large elastic continuum. The application of linear elasticity to this distortion results in a well- known formula for the energy and an expression for the concomitant entropy change due both to the shear strain in the continuum and also to the dilation of the solid resulting from the boundary conditions at the surface of the solid. Elastic data (the sliear modulus and its temperature coelficient) are used to calculate the entropy and energy of formation for many metals. Despite the simplicity of the assumptions involved, the agreement between the calculated entropies and energies and experimental values is remarkably good. In recent years there has been a large increase in measurements of the absolute concentration of mono-vacancies in metals as a function of temperature. Hence new data for both the energy and the noncon-figurational entropy of formation of monovacancies has become available. Recent measurements&apos; of the anomalous (non-Arrhenius) self-diffusion in many bcc metals has also focused interest on the prediction of the thermodynamic parameters of mono- and multi-vacancies in those metals for which no data are available. Damask and Dienes&apos; have discussed the various theoretical calculations of the energy of formation EL, of a monovacancy. These include simple models involving the breaking of atomic bonds on moving atoms from the interior of a crystal to the surface, models combining elastic calculations with surface-energy terms and detailed quantum mechanical calculations. The simler models give the correct order of magnitude of &, but tend to overestimate it by a factor of about two. The quantum mechanical calculations4"7 have been carried out for the noble and alkali metals with generally reasonably good agreement with the available Ef data. The calculation of entropy of formation Sfv14 lnvolves a fundamental calculation of the perturbation of the phonon spectrum caused by the creation of a vacancy. Huntington, Shirn. and wajda8 have given an approximate evaluation of sJV by considering an Einstein model for the localized vibrations in the immediate neighborhood of the defect and then using elastic theory to calculate the entropy associated with the shear stress field in the distorted crystal (as originally proposed by Zenerg). They also included a term due to the dilation of the crystal. They obtained a value of 1.47k for copper, in good agreement with the experimental value (1.50k). However, Nardelli and Tetta- manzi1° have recently shown that neglecting the coupling between atoms (Einstein Model) may lead to a serious error so the agreement may be somewhat fortuitous. In this work simple linear elastic theory is used to calculate the entropy and energy of formation of mono-vacancies. Despite the simplicity of some of the assumptions involved, the agreement with the available experimental data is remarkable. However. the reasonable degree of success in the application of linear elastic calculations to the excess entropy of a solute atom in a dilute solid solution1&apos; indicates that the application of elastic theory to vacancies. where the interaction of different atomic species is not involved, may not be inappropriate. THE ELASTIC MODEL The metal is assumed to be a spherical elastic continuum. A small spherical cavity of volume V = 4i;v:&apos;/3 is cut from the center. removed. and dissolved rever-sibly in the bulk of the material. TO a good approximation no net atomic bonds are broken and the material does not undergo a volume change although the externally measured volume of the body would increase by V. The radius of the sphere of metal is much larger than r Next a negative pressure is applied to the cavity causing its surface to be displaced inward by an amount simulating the relaxation of the lattice around a monovacancy. In this model the energy and entropy accompanying the distortion are taken as 4, and <. As a first approximation the equation of state for the solid is taken as: r = ro(i + *~D LiJ where K is the bulk modulus. P the hydrostatic pressure. Vo the volume of the material at 0°K and zero pressure. and d+/dT = 30. where 0 is the linear thermal expansion coefficient. The variation of entropy with hydrostatic pressure is given by the Maxwell equation: These equations give the entropy change resulting from increasing the hydrostatic pressure from 0 to P as: and since • we have: This is the entropy arising from the dilation resulting

Jan 1, 1970

By J. Chipman, G. G. Hatch

One of the important functions of the iron blast furnace is the desulphur-ization of pig iron before it enters the steelmaking furnaces. However, the increasing concentrations of sulphur in the metallurgical coke, source of approximately 90 pct of the sulphur present in the blast furnace charge, and demands for higher rates of production within recent years have increased the need for greater desulphurization within the iron blast furnace. Furnace operators are beginning to look for desulphurizing agents other than blast furnace slag to accomplish the desired degree of desulphurization. A considerable amount of work has been done on desulphurization outside the furnace with soda ash, calcium carbide and various synthetic slags. Whether the desulphurization of pig iron is accomplished wholly inside the furnace or partly inside and the remainder outside, will be determined by the economics involved. Regardless of which is the case, it is believed that it is necessary to have a better understanding of the physical chemistry of desulphurization by blast furnace slags. To this end, it is the object of the present investigation to attempt what is believed to be the first equilibrium study of the distribution of sulphur between liquid pig iron and a wide range of blast furnace slag compositions. Review of Literature There is a considerable amount of information in the literature concerning the desulphurizing power of iron blast furnace slags, the solubility of various sulphides in the slags, and the effect on desulphurization of temperature, of elements dissolved in the liquid iron, and of viscosity. However, there is nothing to indicate that the equilibrium distribution of sulphur between liquid iron saturated with carbon and iron blast furnace slags has been studied experimentally. Wentrupl has made probably the most detailed study of the desulphurization of pig iron to date. He considered that there are three distinct aspects involved, namely: 1. Desulphurization within the blast furnace (by lime and manganese). 2. Subsequent desulphurization by manganese. 3. The effect of subsidiary reactions on the desulphurization by manganese. The experimental work carried out by Wentrup was devoted mainly to obtaining a better understanding of how desulphurization by manganese was accomplished in the mixer and the ladle. Particular attention was given to the part played by carbon, silicon, and phosphorus associated with manganese in the iron, and the effect of temperature on desulphurization. The experimental results indicated that desulphurization by manganese is purely a process of crystallization of manganese sulphide. The addition of silicon to iron melts containing 3.5 pct carbon and less than 0.5 pct manganese had no noticeable effect on desulphurization, but with 1-2 pct manganese the silicon additions improved the desulphurization. Additions of phosphorus also resulted in improved desulphurizati011 by manganese, but the effect was not as marked as in the case of silicon. It was also found that desulphurization by manganese was further improved by lowering the temperature. In order to explain desulphurization inside the blast furnace, Wentrup considered the system iron, sulphur, calcium, oxygen, manganese. (silicon). The distribution of sulphur between the metal and slag was represented by the following equation: (SS) _ (S)Fe + (S)Ca + (S)Mn .... [S] = [s] [1] The parentheses and the brackets represent the equilibrium concentrations in weight per cent of the slag and metal constituents, respectively. Since FeS D (FeS) _ (FeS) (S)Fe LfeS - [FeS] [S] [2] (CaO) + S e (FeO) + (S)Ca _ (FeO)(S)Ca. (S)Ca _ (CaO) Kl = (CaO)[S] [S] ~K1(FeO) [3] Mn + S D (S)Mn (S)Mn (S)Mn K&apos; = [MnpT "1ST = *lIMnJ !4) Substitution of Eq 2, 3, and 4 into Eq 1 resulted in if = L- + *> (Sol + K^ (S) [51 Eq 5 was used to calcu1;lte -f^j and [S] at 1480°C for slags containing 30-50 pct lime, 0.1-2.5 pct iron oxide, 0-26 pct silica, 2 pct sulphur and iron analyzing 1.5 pct manganese. The value for LFaB at 1480°C was found to be equal to 4.5, based on the experimental work of Bardenheuer and Geller.2 The results of the calculations are shown in Table 1. Although the slags are hypothetical and do not represent the range of compositions found in ordinary blast furnace practice, the calculations indicate that lime is effective in controlling desulphurization only if the iron oxide and silica contents of the slag are kept low. Schenck3 did not claim K1 to be a true equilibrium constant, but an empirical value which varied with the silica content of the slag.

Jan 1, 1950

By M. Kitada, U. Kawabe, F. Ishida, T. Doi

The relations between micros tructures and critical current density in transverse magnetic field were experimentally investigated due to each transformation of the 0 to 0&apos; + P" phases at 700&apos; C for superconductmainly examined using replication electron microscopy. The ß&apos; or a precipitates were found to pin down magnetic flux lines in these alloys. The effects of precipitation upon the critical current density were discussed in relation with the size, spacing, and characler of these precipitates. HIGH magnetic field superconductors, such as Nb-Zr, Nb-Ti, and Nb-Zr-Ti alloys, have been recently put to extensive practical use as winding materials for superconducting magnets.13 The critical current density of these hard superconductors under an applied magnetic field is an important characteristic for magnet materials and is very sensitive to metallurgical structure. It is generally known that the critical current density is increased by introducing dislocations and precipitates into a superconductor; that is, dislocations and precipitates are presumed to be barriers that hinder quantized flux lines from moving.4&apos;5 Theoretical6&apos;7 and experimental analyses of the motion of flux lines and the interaction between flux lines and various defects have already been reported by many authors. Metallographic analysis of high magnetic field superconductors such as Nb-Zr and Nb-Ti is difficult, so that no quantitative relationship between microstruc-ture and critical current density has been established yet. In this paper, the effect of precipitation on the critical current density in magnetic field was investigated for two superconducting alloys, Nb-40Zr-10Ti and Nb-5Zr-60Ti. In these alloys the resistive critical field H, at 4.2oK was about 100 kG and the critical current density Jc at 80 kG was of the order of 104 amp per sq cm.13-l5 The superconducting properties were examined in relation to the microstructural changes due to transformation of i) the ß to ß&apos; + ß" phases at 700°C for Nb-40Zr-10Ti alloy and ii) the ß to a + ß phases at 500°C for Nb-5Zr-6OTi alloy. The effect of size, spacing, and character of precipitates on flux line pinning was in particular examined. The microstructures were studied by means of residual resistivity, microhardness, and tensile strength measurements as well as by X-ray diffraction, optical, and replication electron microscopies. I) EXPERIMENTAL PROCEDURE Pure niobium, zirconium, and titanium, in the form of rods 0.8 cm in diam, served as raw materials. Results of chemical analyses of these rods are given in Table I. Ingots of the alloys, 0.4 cm in diam and 3 cm in length, were prepared by means of levitation melting, utilizing a copper mold in an argon-gas atmosphere. Samples from the ingot then were cold-worked by grooved mill to 0.2 cm in diam, heat-treated homogeneously (in the ß phase region) for 5 hr at 1100° in a vacuum of 1 x 106 Torr, and finally cold-drawn to 0.025 cm in diam. For heat treatments, samples were wrapped in niobium foil and sealed in an argon-gas atmosphere in fused quartz capsules. Water quenching was done after each heat treatment. Subsequently H-J, were performed at 4.2° by slowly transporting the current through the samples 4 cm long, under transverse magnetic field, until the least detectable resistive terminal voltage was observed. The resistive critical field H, was taken as the field at which 100 pv appeared at 4.2°K across a sample 3 cm in length, with a current of 5 ma. The critical temperature T, was measured by means of a conventional four-probe resistivity technique and taken as the temperature at which the sample resistance reached one-half of full restoration of the normal-state resistance with a current l ma flowing through a sample 2 cm in length. Precipitates were observed by means of optical microscopy and carbon replication electron microscopy. The etching solution consisted of 5 ml HF, 10 ml H2SO4 10 ml H2O2, and 50 ml H2O, and shadowed carbon replicas were examined in a itachi HU-11 electron microscope operated at 50 kv. X-ray diffraction photographs were taken by a 11.46-cm-diam Debye-Scher-rer camera using copper Ka radiation. The micro-hardness was measured under a load of 200 g using

Jan 1, 1969

By Susan T. Bagley, Kenneth L. Rubow, David H. Carlson, Bruce K. Cantrell, Winthrop F. Watts

Permissible exposure limits (PELs) have been established for gaseous pollutants, carbon monoxide (CO), carbon dioxide (CO2), nitric oxide (NO), nitrogen dioxide (NO2), and some gas-phase hydrocarbons emitted in diesel exhaust. There is, as yet, no PEL recommended for diesel exhaust aerosol (DEA), nor is there a standard method for sampling this aerosol. The University of Minnesota and the U.S. Bureau of Mines have collaborated to develop a personal diesel exhaust aerosol sampler (PDEAS) which utilizes size-selective inertial impaction and gravimetric analysis. During the field tests of this sampler, numerous air quality measurements were made in underground coal mines that use diesel equipment. The mine mean DEA concentrations for the five mines surveyed, determined with the PDEAS in the haulageway, was 0.89 mg/m3 with a standard deviation of 0.44 mg/m3. DEA contributed 52 % of the respirable aerosol at this location. In three of the mines filter samples were collected for DEAassociated polynuclear aromatic hydrocarbons (PAHs) and biological activity determinations. Two of the mines were also monitored for the major gaseous constituents found in diesel exhaust. In general, the PAH and biological activity levels were similar for all three mines, and indicate that up to 25 % of the haulageway concentrations may be contributed by outby diesel vehicles. Measured concentrations of CO, C02, NO, NO2, and SO2, were well below regulated levels. INTRODUCTION Diesel exhaust contains pollutant gases, such as carbon monoxide, carbon dioxide, nitric oxide, nitrogen dioxide, and gas-phase hydrocarbons, as well as DEA. Much of the health-related concern focuses on DEA and associated organic compounds (Watts, 1992a). A wide variety of these PAHs have been identified and some are known carcinogens and/or mutagens. The U.S. Mine Safety and Health Administration (MSHA) has proposed new PELs for these and other contaminants (MSHA, 1989). MSHA has also published an advance notice of proposed rulemaking to establish a separate PEL for diesel particulate (MSHA, 1992). The U.S. Bureau of Mines has collaborated with the University of Minnesota to develop and field test a PDEAS. The PDEAS is a three stage sampler based on the MSA&apos; personal respirable dust sampler. It utilizes a respirable cyclone preclassifier followed by a 0.8 µm cut point impactor and afterfilter operating at a flow rate of 2 L/min. Respirable aerosol greater than 0.8, µm in size is collected by the impactor while DEA, less than 0.8 µm in size, is collected by the afterfilter. Hence, gravimetric analysis of the afterfilter permits measurement of DEA concentrations. This development and laboratory evaluation of the PDEAS were described previously by Cantrell (1990) and Rubow (1990). During field tests of the sampler, numerous air quality measurements were made in continuous miner sections of five underground coal mines that use diesel haulage equipment. These air quality measurements included levels of selected PAH and biological activity associated with DEA collected in the intake and haulageway areas of three of the five underground mines, and CO, CO2, NO, and NO2 in two of the mines. The objectives of this paper are to present the DEA and associated pollutant concentrations measured in these mines and to assess the impact of diesel face-haulage equipment on underground mine air quality. MINE DESCRIPTIONS The mines used for the PDEAS evaluation were designated J, K, L, N, and 0. Mines K, N, and 0 are located in the Western United States, while mines J and L are located in the East. Each mine produces high volatile, bituminous coal with shift production levels varying from 500 to 2000 tons/section. Seam heights varied from 1.5 to 3.0 m. Mines K and N use continuous mining to develop longwall panels. The others are strictly room-and-pillar operations using continuous miners. The number and types of diesel-powered vehicles used at these mines were described by Watts (1992b). Mines J, K, N, and 0 use diesel power to assist in a wide range of activities in addition to coal haulage. These included road maintenance, personnel and materials transport, lubrication, and welding. Mine L used only three diesel-powered shuttle cars to haul coal. SAMPLING AND ANALYSIS METHODS Aerosol Measurements Aerosol samples were collected in the mine portal area, the clean air intake to the continuous miner section, the haulageway one crosscut inby from the feeder breaker and belt, in the return airway, and on selected personnel. The haulageway sampling site was located near the point where the diesel-powered shuttle cars turn around to dump their loads. Additional respirable and DEA samples were collected and have been reported by Haney (1990).

Jan 1, 1993

By P. A. Witherspoon, S. P. Neuman

Evaluating the permeability of a caprock overlying a potential gas storage reservoir is a very critical problem. Pumping water from the reservoir can be used as an evaluation tool in analyzing this problem. Fluid level changes that occur in the aquifer us well as in the caprock can be measured with appropriately placed wells. If the leakage of water from the caprock into the aquifer is considerable, the effects will be apparent in the aquifer. If the leakage is slight, however, it will not be possible to detect it with certainty from observations in the aquifer alone. Fluid level measurements in the caprock must be relied upon. and improved methods of analyzing such effects have been developed which are based on a theoretical analysis of fluid flow through a caprock of infinite thickness. An example applying these methods to field data is discussed. INTRODUCTION One of the most critical problems in evaluating an aquifer gas storage project is determining the tightness of the caprock overlying the formation to be used as the storage reservoir. A formation that has previously held oil or gas obviously has a suitable caprock, but an aquifer that contains only water gives no such assurance. A number of aquifer projects in the United States have been troubled by gas leaking out of the intended storage zone, and the ensuing difficulties have led to the development of new evaluation methods. One of these new methods is pump testing wherein water is removed from the aquifer at some controlled rate prior to injection of gas. This fluid withdrawal causes a pressure drop to move out through the aquifer for considerable distances in a matter of days or weeks. Depending on the properties of the caprock, a pressure transient can also pass upward (as well as downward) through the caprock layers adjacent to the aquifer. Thus, if the operator has placed observation wells at appropriate distances from the pumping well, the rapidity with which the pressure transients reach different points in the system can be used to investigate the fluid transport properties of both the aquifer and its caprock. The usefulness of pump testing has been recognized by groundwater hydrologists for many years as a means of determining the potential yield and properties of aquifers used in water supply They have introduced the term "leaky aquifer" for a system in which an aquifer is overlain (or underlain) by semipermeable caprock layers. The ease with which water leaks into the aquifer during pumping can, of course, be very beneficial in bringing additional water to the pumped well. Hydrologists have therefore devoted considerable attention to this prob-lem. From the gas storage standpoint, however, the tighter the caprock layers that overlie the intended storage reservoir, the better are the conditions for minimizing or eliminating any vertical migration of gas. Thus, after a suitable geologic structure has been found, the emphasis in aquifer storage projects is in determining that the caprock is tight. Attention has recently been focused on the use of pump testing as one approach to solving this problem.23,24 This paper presents a further development on evaluating the permeability of a slightly leaky caprock when the caprock is of infinite thickness. From the practical standpoint, this means that the caprock layers are thick enough that pressure transients do not reach the outer boundaries of the system during the pumping test. In a subsequent paper, an analysis of the case where the caprock is of finite thickness will be presented. PREVIOUS WORK ON LEAKY AQUIFERS Jacob" developed a partial differential equation describing the flow of water in an aquifer of permeability k that is overlain by a leaky caprock of permeability k&apos;. Fig. 1 shows a schematic cross-section of the system under consideration. One of his principle assumptions was that if k > > k&apos;, the direction of flow is essentially vertical in the caprock and horizontal in the aquifer. Neuman19 confirmed the validity of Jacob&apos;s assumption using a mathematical model. Another assumption was that a permeable source layer overlies the caprock (Fig. 1) and is able to maintain a constant hydraulic head at the upper boundary of the caprock. By neglecting the effects of compressibility within the caprock, Jacob1* developed a solution for a bounded circular aquifer. Later, Hantush and Jacobx5 used the same assumptions to solve the case of an infinite radial aquifer that is pumped at a constant rate. Their solution may be expressed in di-mensionless parameters by

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,&apos; in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.&apos; have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.&apos; Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.&apos;&apos;-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By T. V. Philip, Paul A. Beck

IN a previous note1 it was pointed out that the available information suggests a distinct correlation between the occurrence of the CsCl-type ordered structures formed in equi-atomic binary alloys of transition elements and the location of the components in the periodic table. A definite increase in the bond strength between unlike atoms, as compared with that between like atoms, is indicated when, in binary alloys of iron group elements, the other component is changed from chromium to vanadium or tantalum, to titanium. Laves and Wallbaum,2 eported a CsCl-type ordered structure for the stable intermediate phase at the equi-atomic composition in the Ti-Fe system (and also in the Ti-Ru and Ti-Os systems). On the other hand, Tagaya, Nenno, and Nishiyama8 found no ordering of this kind in the body-centered-cubic solid solutions in the Cr-Fe system. It was concluded&apos; that the occurrence of a CsC1-type ordered phase of intermediate stability may be expected in the V-Fe system. Preliminary results were described: suggesting that at least some degree of order does exist in the equi-atomic alloy VFe, annealed at 1200° C and quenched in cold water. Using CrK radiation, at least one weak superlattice line was found in the X-ray diffraction pattern which could be indexed as (100). and which disappeared, as expected, when FeK radiation was used. It was found more recently that the impurity phase (presumably VN), previously giving rise to additional X-ray diffraction lines and thus preventing definite indentification of the (111) superlattice line,&apos; can be eliminated by preparing the alloy by arc melting in a helium atmosphere. The alloy specimen melted in this manner had clean surfaces and showed very littte, if any, nitride phase in the microstructure after annealing in vacuum at 1250°C and quenching. The relative intensity of the (100). superlattice line with CrK radiation was greatly increased and, in addition, a fairly strong (Ill) , superlattice line and even a detectable (210) , super- lattice line was obtained, when the powder produced by filing from the 1250°C annealed and quenched specimen was reannealed in vacuum at 625°C for 1 hr. By using a cellulose acetate film as a filter in front of the photographic film in order to absorb the soft radiation resulting from air fluorescence, the background intensity could be reduced considerably in relation to the intensity of the diffraction lines. All three superlattice lines, (100),, (111)., and (210)a, disappeared, as expected, when a radiation other than CrK, was used.1 For the powder reannealed at 625ºC, the strongest lines of the s pattern also appeared weakly, indicating that during an: nealing at 625°C a small amount of transformation took place from the body-centered-cubic to the u phase. However, since all superlattice lines to be expected in the 0 angle range used were actually very clearly present, it was evident that the high temperature body-centered-cubic phase had transformed into a CsCl-type ordered structure before much s phase could form. Reannealing filings for 1 hr at 700°C resulted in complete transformation into the u phase. After 1 hr at 650°C the transformation into IT was not quite complete, the strongest body-centered-cubic diffraction lines were still present, although fairly weak, and only the (100), super-lattice line was detectable (extremely weak). These findings not only confirm the previous conclusionsL as to the existence of a CsCl-type ordered structure in the Fe-V system, but they also indicate that this metastable ordered structure forms at about 600°C preceding the formation of the stable s phase, while at 1250°C the disordered body-centered-cubic phase is stable. The faint (loo) , super-lattice line previously observed in specimens quenched from 1200°C was probably due to the fact that the quenching of the powder in an evacuated fuse:! quartz capsule was not fast enough to prevent completely the ordering reaction on cooling. The present results conform with the suggestion that the A-B bond, in relation to the A-A and B-B bonds, increases in strength from CrFe to VFe to TiFc. It is, therefore, of interest to compare the measured values of the average atomic diameter for these three alloys with the corresponding average atomic diameters calculated from the atomic radii of the elements concerned. ASSUming A-B contacts

Jan 1, 1958

By R. L. Skaggs, D. T. Peterson

The effect of carbon in solid solution on the plastic behavior of thorium was studied by measuring the flow stress of Th-C alloys from 4.2" to 573°K and at several strain rates. Carbon was found to strengthen thorium primarily by increasing the thermally activated component of the flow stress. The strengthening due to carbon was directly proportional to the carbon content and decreased rapidly with increasing temperature up to 423" K. The flow stress also increased with increasing strain rate. The strengthening appears to be due to a strong short-range interaction between carbon atoms and dislocations. A yield point was observed in the Th-C alloys which increased with increasing carbon content. JTREVIOUS study of the mechanical properties of thorium has been confined largely to the measurement of the engineering properties. Work prior to 1956 has been summarized by Milko et al.1 who reported that additions of carbon to thorium sharply increased the room-temperature strength. In addition, the yield strength was observed to decrease rapidly over the temperature range from 25" to 500°C. In 1960, Klieven-eit2 measured the flow stress of thorium containing 400 ppm C. He found that over the temperature range from 78" to 470°K the flow stress was strongly dependent on temperature and rate of deformation. A drop in the load-elongation curve, or a yield point, was observed over most of the above temperature range. Above 470°K, the flow stress was nearly independent of temperature and strain rate. This strong temperature and strain rate dependence of flow stress is not generally observed in fcc metals. It is, in fact, more typical of the behavior reported for bcc metals. Bechtold,3 Wessel,4 and conrad5 have pointed out the striking difference between the commonly studied bcc metals and fcc metals in regard to the effect of temperature and strain rate on the flow stress. Zerwekh and scott6 studied the plastic deformation of thorium reported to contain 12 ppm C. They found that this material did not obey the Cottrell-Stokes law as expected for fcc metals. In addition, they found values of the activation volume smaller by an order of magnitude than expected for an fcc metal. They concluded that thorium was strengthened by a randomly dispersed solute. Thorium differs from many other fcc metals that have been studied extensively in that it shows a relatively high carbon solubility at room temperature. Mickleson and peterson7 report the solubility limit at room temperature to be 3500 ppm C. The lowest value reported is that of Smith and Honeycombe8 who report the limit to be 2000 ppm C at 350°C. The pres- ent investigation was a systematic study of the flow stress and yield point phenomenon of thorium over a broad range of carbon content, temperature, and strain rate. EXPERIMENTAL PROCEDURE The thorium used in this investigation was produced by the reduction of thorium tetrachloride with magnesium as described by Peterson et a1.&apos; Chemical analysis of the original ingot after arc melting and electron beam melting is shown in Table I. Alloys were prepared by arc melting this thorium with high-purity spectrographic graphite. Threaded specimens with a gage length 0.252 in. diam by 1.6 in. long were used for the constant stress or creep measurements. These specimens were machined from rod which had been cold-rolled and swaged to % in. diam. Tensile specimens were prepared by swaging annealed 3/8 -in.-diam rod to 0.102 *0.001 in. The as-swaged wire was cut to lengths of 2 in., annealed, and the center 1-in. gage length elec-tropolished to 0.100 ±0.001 in. The specimens were gripped for a length of 3 in. at each end by a serrated four-jaw collet which was tightened by a tapered compression nut. No slipping occurred in the grips and negligible deformation was observed outside the 1-in. gage length. Both the creep and tensile specimens were annealed at 730°C under a vacuum of 1 x X Torr. The resulting structures consisted of equiaxed recrystallized grains with a grain size of 3200 grains per sq mm for the tensile specimens and 2200 grains per sq mm for the creep specimens. After the specimens were prepared, samples were analyzed for nitrogen, oxygen, and hydrogen. The results of these analyses are given in Table 11.

Jan 1, 1969

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah&apos; in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.&apos; studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.&apos; studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h&apos;hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By J. P. Zannaras

Referring to the article by R. J. Charles and P. L. de Bruyn, let us assume that W = weight of glass bar; P = weight of hammer; e = total deformation; K = unit of deformation; K = potential stress energy; E = modulus of elasticity; L = length of the bar; 7 = coefficient of inertia; h = height, ft; V = velocity, fps; and a = cross section area. The portion of kinetic energy which is effective in producing stress energy in a fixed bar struck horizontally is given by the formula" 1 + 1/3 W/P K =1+1/3w/p/(1+1/2w/p)2 P.V2/2g = Ph where 1 + 1/3 W/P ? (1 + 3W/P/(1=1/2w/p)2 [8] Putting e e = W/P =------------ From the above equation it can be seen that the maximum transfer of kinetic energy to stress energy is when e = 0 or W/P = 0 which indicates that the weight of the hammer must be very large as compared with the weight of the impacted rod. Eq. 8 diametrically opposes the conclusions reached by the authors of this article. In fact, if their suggestions were followed to the extreme when e = co when P = 0, there would be no transfer of kinetic energy to stress energy at all, as 7, becomes zero. Eq. 8 presumes that the velocity with which the stress is propagated through the bar is infinite, whereas the authors claim that the compression waves reflected are reaching the struck end of the bar prior to the complete transfer of the kinetic energy to cause such modification of the conditions there as to make them reach the reverse conclusions demonstrated by the above formula. That such interference exists is unquestionably demonstrated by the authors and others. However, if my observations are correct, such interference for this specific experiment and also for practical comminu- tion is insignificant, and the conclusions of the authors are in error and must be reversed to comply with Eq. 8. Eq. 5, w. = AE 2/2, given by the authors on page 51, is derived from the following equation (Eq. 9): K = 1/2Pe, where P = Sa, S = ?E, e = EL, and L = 1. The above formula, Eq. 9, cannot be applied in this case. This formula is applicable for static loads where the load increases from zero up to its final value, P, in such a way that the deformation at different instants is proportional to the loads acting at those instants and actually represents the area of a right triangle in the strain load diagram of base e and height P. The typical photographs shown in Figs. 3 and 4 represent the familiar strain load diagrams, and since the line of the wave marks the existence and intensity of the strain with the unquestionable conclusion that such strain has been caused by the action of a load acting continuously all along the wave until it reached the horizontal axis, the work stored at this point is represented by the area under the wave line and the horizontal axis and not by the area of the fictitious triangle given by the authors. Then if this is correct, even visual estimation of these areas at gage stations given in the typical photographs of Figs. 3 and 4 suffice to contradict the authors&apos; calculation given in Figs. 6a and 6b and Figs. 7a and 7b. The typical photographs presented by Charles and de Bruyn show a considerable variation of the intensity of the strain at different stations but very small variation of areas which actually represent the stress energy at the corresponding stations. And, apparently, by squaring the small quantities, the authors magnified their error tenfold. J. M. Frankland&apos;s paperV iscusses the relative strain intensity and not the total energy for different types of impact loading. He states in his paper, "The reader is explicitly warned not to confuse the results in this report with those obtained when the load is applied by a blow as from a hammer. In this case the peak load rises to very large but mostly unknown values. The accompanying large deflections and stresses are the result of high values of P, not of the dynamic load factor n. According to Frankland "the dynamic load factor" is the numerical maximum of the response factor. It therefore appears that the authors followed the same procedure in obtaining the relative strain energy ab-

Jan 1, 1957

COUNCIL AND STANDING COMMITTEES - 1973-1974 Office Bearers: P. W. J. van Rensburg (President), Professor R. P. Plewman and Dr R. E. Robinson (Vice Presidents), J. K. E. Douglas (Honorary Treasurer), and Dr J. P. Hugo (Immediate Past President). Elected Members of Council: Dr M. G. Atmore, G. H. Grange, Dr P. R. Jochens, J. G. Kirchner, Dr D. I. Legge, W. W. Malan, Dr M. D. G. Salamon, L. W. P. van den Bosch, D. A. Viljoen, P. A. von Wielligh. Branch Chairmen: B. T. Hosking (Witbank-Middelburg Branch), E. T. Wilson (Orange Free State Branch). Past Presidents Serving on Council: R. J. Adamson, M. Barcza, H. Britten, H. E. Cross, Professor J. de V. Lambrechts, R. C. J. Goode, Professor D. D. Howat, D. M. Jamieson, D. G. Maxwell, Dr J. T. McIntyre, V. C. Robinson. Ten Council meetings were held during the year, with an average attendance of 19, and the standing committees held 30 meetings. COMMITTEE CHAIRMEN Membership, Dr R. E. Robinson ; Metallurgical Colloquia, Dr R. E. Robinson ; Mining Colloquia, L. W. P. van den Bosch; Awards, P. W. J. van Rensburg; Excursions, P. A. von Wielligh; Dinner, G. H. Grange ; Constitution, Rules and Policy, Dr J. P. Hugo; Adjudicating, P. W. J. van Rensburg; Mines and Works, W. W. Malan; Education, Dr J. P. Hugo. REPRESENTATIVES ON OTHER BODIES Associated Scientific and Technical Societies: Members : V. C. Robinson and D. G. Maxwell Alternates : P. W. J. van Rensburg and Dr J. P. Hugo. Federation of Societies of Professional Engineers Members : J. K. E. Douglas and P. W. J. van Rensburg Alternates : Dr J. P. Hugo and G. H. Grange. South African Council for Professional Engineers Members : R. C. J. Goode and J. K. E. Douglas Alternates: G. H. Grange and Dr R. E. Robinson. Engineers&apos; Liaison Committee (Pretoria): Member: Professor J. de V. Lambrechts Alternate : Dr J. P. Hugo. MEMBERSHIP Seventeen Fellows and Members, twenty-three Graduates, ten Associate Members, twenty-two Associates, thirty-four Students, and seven Company Affiliates were elected during the year. Eleven Fellows and four Members were admitted to retired membership. Five Fellows were elected to Honorary Life Membership. Four Members, two Graduates, and one Student were transferred to Fellows ; eleven Graduates and Students were transferred to Members ; eight Students to Graduates; and four Students to Associates. A statement of membership as at June 30th 1974 and the end of the previous year is given in the following tabulation 30th - 30th June, - June, 1973 - 1974 Honorary Life Fellows 4 - 9 Honorary Fellows 9 - 8 Life Fellows 177 - 170 Fellows 536 - 544 Members 487 - 512 Associate Members - - 10 Graduates 128 - 130 Associates 186 - 194 Students 183 - 173 Company Affiliates 64 - 70 1 774 - 1 820 OBITUARIES Your Council records with deep regret the death during the year of the following members : Dr P. N. Lategan and Dr O. A. Jackson, Honorary Life Fellows and Past Presidents; C. Airth, T. L. Blunt, J. B. Dennison, A. E. Frazer, C. L. Lamb, V. O. Reid, K. Richardson and D. G. Roberts, Life Fellows ; H. F. Allan, J. T. Beaumont, M. Eisenstein, J. C. Hall, C. F. Louw, H. H. McGregor, R. Murchison, and J. E. Williamson, Fellows; and R. B. Miles, Associate. FINANCE The annual accounts, which follow this report, reflect a healthy position and show that measures taken by Council over the last few years to boost income have been successful. A higher income was needed not only to meet rising costs but also so that the services provided by the Institute for its members could be expanded. This year&apos;s income of R55 025 showed a further increase compared with last year&apos;s figure of R48 307. Income from subscriptions was higher mainly owing to an increased number of Company Affiliates, and this is indicative of the support given by mining and metallurgical companies to the good work being done by the Institute. Further sales of publications of the symposia held over the last few years again made a useful contribution to income of R4560. The first Winter School held in 1973 yielded a surplus of R7495 after the expenses had been deducted from the income received from registration fees. The cost of administering the Institute increased by R2212 compared with the previous year. Included in this was a donation of R1000 to the A.S. & T.S. Trust Fund. The cost of publishing and printing the Journal increased by R2034, but advertising and extraneous sales of the Journal were higher, with the result that the net cost of the

Jan 10, 1974