Search Documents

By J. W. Cuthbertson, R. A. Cresswell

THE constitution of Cu-rich alloys with 1.5 to 13.5 pct Sn and 0.25 to 3.0 pct Be and the precipitation-hardening characteristics of alloys with 1.5 to 13.5 pct Sn and 0.25 to 1.0 pct Be have been examined. The hardness and tensile strength of the alloys examined increase markedly after solution treatment at 700°C followed by heat treatment at temperatures between 200" and 450°C. By a combination of cold work and heat treatment, hardness values similar to those exhibited by commercial Be-Cu alloys containing 2.25 pct Be can be obtained with ternary alloys containing 9 pct Sn and 0.75 pct Be and containing 10 pct Sn and 0.5 pct Be. Marked hardening effects occur with alloys containing even less beryllium. By heat treatment alone, a hardness value of 310 diamond pyramid hardness can be obtained from an alloy containing 10 pct Sn and 0.75 pct Be. Preliminary tensile tests have shown that an ultimate tensile strength of 110,000 psi with an elongation of 23 pct is obtainable by precipitation hardening an alloy with 8 pct Sn and 0.75 pct Be. The precipitation-hardening process has been followed microscopically for certain alloys and the inference is that, while the initial hardening effect is probably explained by the precipitation of the ß phase of the Cu-Be system, further hardening, proceeding at a much slower rate, also occurs, apparently as a result of precipitation of phases of the Cu-Sn system, particularly precipitation of the 6 phase at temperatures below 350". The presence of the e phase of the Cu-Sn system in certain alloys at temperatures below 350°C has been confirmed. Tin-bronzes are widely used in engineering applications where a combination of high strength and good resistance to corrosion is wanted. The maximum strength is induced in these alloys by cold working, and it would be an advantage for many purposes if high strength could be achieved alternatively by an age-hardening process. While Cu-Sn alloys have a good fatigue resistance they can be surpassed in this respect by Cu-Be, but the use of the latter alloy is limited by its high cost. If, by adding beryllium to tin-bronze, the properties of the respective binary alloys could to some extent be combined, a most attractive alloy should result. As pointed out by Raynor,¹ beryllium is on the borderline of the zone of favorable size factors for copper, and the solid solubility of beryllium in copper is consequently much more restricted than if the size factor were strongly favorable. The size factor is sufficiently favorable, however, to permit an increase in solid solubility with rise in temperature, and there is thus a composition range in which CU- Be alloys are susceptible to hardening by precipitation heat treatment. Although the a phase of the Cu-Sn system is similarly susceptible to precipitation treatment, the time necessary to establish equilibrium in commercial alloys of this type is usually so great that age hardening becomes impracticable. The addition of beryllium to Cu-Sn alloys would appear to offer a means of conferring on the latter useful age-hardening properties. Masing and Dahl² and others have, in fact, shown that the addition of beryllium to Cu-Sn a solid solutions renders these alloys susceptible to precipitation hardening and after such hardening confers on them an encouraging improvement in physical properties. If this improvement could be achieved by the addition of substantially smaller amounts of beryllium than are customarily found in binary Cu-Be alloys, the ternary alloys should possess economic advantages which might make them more attractive than the binary alloy for some applications. Binary Systems Copper-Tin: The constitution of these alloys is now reasonably well known and is summarized in the equilibrium diagram published by Raynor.³ The following observations, due to Raynor,¹ on the structure of those phases of the Cu-Sn system that are likely to be found in the ternary alloy system will facilitate the subsequent discussion on the examination of that system. The ß phase is an electron compound at the electron-atom ratio 3:2 and has a body-centered cubic crystal structure. This phase is stable only down to 586°C, at which temperature it decomposes eutectoidally into the a and y phases. The y phase has a structure that is also based on the cubic system. This phase is stable down to 520°C, at which temperature it decomposes eutectoidally into the a and d phases. The d phase is an electron compound (Cu³¹Sn8) which has a crystal structure analogous to that of 7 brass. This phase is stable from 590" to 350°C; on prolonged annealing at the latter temperature it breaks down into a mixture of the a and E phases. The e phase is an electron compound (Cu³Sn) having the electron-atom ratio 7:4. Its structure may be regarded as a superlattice based on the close-packed hexagonal system. This phase is stable from 676°C to room temperature. The primary solid solubility of tin in copper increases to a maximum of 15.8 pct as the temperature falls from that of the peritectic reaction to 586°C. The solid solubility remains constant from 586" to 520°C. At lower temperatures the solubility decreases progressively. Below 350°C the fall in solubility is pronounced and is associated with the precipitation of the e phase. This precipitation is very sluggish and does not normally occur under service conditions. Copper-Beryllium: The Cu-Be system has been investigated by Borchers' and others. Raynor5 summarized the present state of information on it.

Jan 1, 1952

By P. T. Brooks

This Bureau of Mines study describes a process for recovering nickel, cobalt, molybdenum, and chromium contained in complex waste superalloy grindings that, for lack of an economical domestic recovery process, are being largely marketed abroad. The process, devised by laboratory scale operations, includes scrap preparation, dissolution of metallics in hot chlorinated acidic liquor, carbon adsorption, three successive solvent extraction separations, and selective chemical precipitations. Nearly 90 percent of the nickel, cobalt, molybdenum, and chromium were separated and recovered as oxides, carbonates, and basic sulfate products.

Jan 1, 1969

By A. E. Raddatz

The Federal Bureau of Mines, as part of its goal to minimize undesirable environmental impacts associated with mineral processing, has investigated a soda-smelting technique for processing ilmenite into pig iron and a titanium slag that is suitable for a feed to a sulfate-process titania pigment plant. By this procedure, the generation of ferrous sulfate waste and its associated disposal problem is obviated. Molten titania slag was quenched, water leached, and filtered to yield a sodium titanate intermediate product containing about 70 wt-pct Ti02, 1 wt-pct Fe, and 20 wt-pct Na20. This intermediate product, high-soda titanate (HST), was mixed with H2S04, calcined, quenched, and water leached to produce a low-soda titanate (LST) product that contained only 2 wt-pct Na20. Both the HST and LST were evaluated as feed materials for preparing titania by the sulfate process. About 95 pct of the Ti02 was extracted from HST and LST by digestion in concentrated or 50-wt-pct-H2S204 solutions. About 95 pct of the solubilized Ti02 was subsequently recovered from the titanyl sulfate solutions by hydrolysis. Barren solutions from hydrolysis, containing about 26-wt-pct H2S04, were upgraded by vacuum-thermal evaporation or electrodialysis. The regenerated acid solutions were used to digest additional HST and LST.

Jan 1, 1979

By Saulo Brinco Diniz

As ligas de alumínio da série 7XXX são largamente utilizadas no setor aeronáutico devido sua alta razão resistência mecânica / densidade. O que proporciona uma alta resistência mecânica para as ligas da série 7XXX é a adição de elementos de ligas e tratamentos térmicos adequados, como por exemplo o T7351. Este trabalho teve como objetivo, estudar a evolução microestrutural de uma liga de alumínio 7475-T7351 processada por laminação convencional a temperatura ambiente, e posteriormente submetida a tratamentos térmicos de recozimento para recristalização. De acordo com os resultados apresentados, a amostra que foi submetida ao tratamento térmico de recozimento para recristalização a temperatura de 500ºC durante 15 minutos recristalizou, enquanto que a amostra que foi tratada a 350ºC durante 1500 minutos teve coalescimento dos precipitados.

Oct 30, 2017

By Darlene Souza da Silva Almeida

Superduplex são aços inoxidáveis bifásicos de alta liga que, para alcançar suas excelentes propriedades mecânicas e de resistência à corrosão necessitam de um rígido controle sobre sua microestrutura, em especial sobre dois aspectos: relação ferrita/austenita e precipitação de fases deletérias. As transformações metalúrgicas que ocorrem durante o ciclo térmico de soldagem podem modificar tais aspectos e, consequentemente, causar grave degradação das propriedades destes materiais. Buscando contribuir na investigação de parâmetros adequados para a soldagem destes aços, o presente estudo tem como objetivo avaliar a influência do aporte térmico e do gás de proteção sobre tais transformações por meio da avaliação da microestrutural final de juntas soldadas. Para isto seis chapas do SAF2507 foram soldadas via processo GMAW utilizando três aportes diferentes (0,5; 1,5 e 2,2 kJ/mm) e dois gases de proteção distintos. Após a soldagem, a microestrutura das juntas foi caracterizada via microscopia óptica e microscopia eletrônica de varredura e os resultados mostraram que o aumento do aporte térmico elevou significativamente a quantidade de austenita tanto na ZTA quanto na ZF e que a utilização de gás de proteção contendo 2% de N causou aumento de até 17,9 pontos percentuais na quantidade média de austenita na ZF. Adicionalmente, observou-se que os dois menores aportes provocaram a precipitação de fases secundárias na ZTA, com morfologia semelhante à nitreto de cromo.

Jan 16, 2018

By Jorge Magalhães Ávila de Paula

A aplicação de materiais metálicos exige que os mesmos sejam submetidos a etapas de conformação mecânica. Estes procedimentos elevam significativamente a densidade de descontinuidades, alterando a morfologia dos grãos, assim como o estado de tensão induzida na estrutura. Os materiais submetidos a processos de conformação, em especial aos de conformação a frio, são submetidos, após a deformação, a um tratamento térmico denominado de recozimento de recristalização, cujo objetivo é recuperar a estrutura e recristalizar os grãos. Neste contexto, estudou-se a viabilidade de aplicação da técnica de calorimetria diferencial (DSC), como ferramenta para a determinação da temperatura de início de recristalização de aços. Para a execução deste trabalho, foram utilizados amostras de aço SAE1010 que foram deformadas a frio e em seguida submetidas a rampas de aquecimento em um equipamento DSC. A técnica de DSC evidenciou apenas o início do fenômeno de recuperação do material. Algumas amostras deformadas foram submetidas a tratamentos térmicos de recozimento de recristalização a 500°C, 600°C e 700°C. A partir da caracterização microestrutural e de ensaios de microdureza, calculou-se os valores de k e n do modelo de Avrami para as amostras tratadas a 600°C e 700°C, obtendo-se após isto a energia de ativação para as deformações de 69,6% (199,5KJ) e 87% (178,4KJ). À 500°C, as amostras não se recristalizaram, confirmando esta temperatura abaixo da crítica para as deformações estudadas.

Aug 16, 2017

By Aprígio Ângelo de Jesus

No presente trabalho, foram avaliados os efeitos do tratamento térmico de alívio de tensões na microestrutura e propriedades mecânicas de juntas soldadas dos aços SA516-70 e SA387-11 (ambos aplicados na fabricação de vasos de pressão). Chapas com 40 mm de espessura de ambos os aços foram soldadas por arco elétrico com arame tubular e, posteriormente, submetidas a tratamento térmico para alívio de tensões. A variação de dureza ao longo da solda e a resistência à tração dos materiais soldados e tratados termicamente foi avaliada. A microestrutura dos materiais soldados foi acompanhada por microscopia ótica convencional. Por meio do tratamento térmico empregado foi possível observar a redução do nível de encruamento nos metais base e zonas termicamente afetadas das juntas em ambos os materiais com aumento de ductilidade no aço SA516-70.

Aug 8, 2018

By Amanda de Angelis Vitoi

Neste trabalho foi estudado o efeito da adição de argônio à atmosfera de nitretação sob plasma sobre a resistência à corrosão do aço inoxidável austenítico AISI 316L. As nitretações foram realizadas em reator a plasma pulsado, a 420°C, por 6 h, adicionando-se 0%, 5% e 10% de argônio à mistura gasosa. Os resultados mostraram que a adição de 5% de argônio promove um aumento na espessura da camada de austenita expandida em relação ao material nitretado sem argônio. Com o aumento da concentração de argônio de 5 para 10%, no entanto, verificou-se a formação de camadas de austenita expandida mais finas e de baixa resistência à corrosão devido à presença de nitreto de cromo em sua estrutura.

Aug 8, 2018

THE slide-rule, as a quick and convenient instrument for performing approximate calculations, is steadily growing more and more into favour with the engineer, and results obtained by it are considered close enough to enable him to satisfactorily dealwith a considerable portion of his work. To the surveyor, however, whose ordinary computations must be as precise as his measurements, the present makes of rule are insufficient, except for a very narrow margin of the scales and for rough work. Few will carry the rule when they can clearly see that it is unreliable for general routine, and the careful surveyor is inclined to look askance at those who do use it, recognizing the temptation there undtmbtedly must be to push it into work that the log book should be called upon to treat. From the fact that a surveyor's duties take him on the surface in all weathers, and underground in many wet and uncomfortable places, where the manipulation of a book of mathematical tables becomes both awkward and patience-trying, an efficient slide-rule must offer the mbst transparent advantages. Again, a surveyor being specially trained to read divided scales quickly and accurately, the slide-rule must commend itself as an apt addition to his outfit.

Jan 1, 1912

By S. S. SHINDE, P. C. JIKAR, N. B. DHOKEY

Mill scale is an oxide waste product of steel mills, containing around 70 percent iron and other allied impurities. In the present context, a dynamic prototype counter-current reactor (CCR) was used for the experimentation and simulation of a particle bed using the discrete element method (DEM). Mill scale was pulverized to ASTM mesh range 140 (106 μm)/+ 270 (53 μm) and oxidized in a CCR to make a single oxide Fe2O3 phase by maintaining the required thermodynamic conditions, such as pure oxygen at 1,100 °C. This oxidized powder was then subjected to a reduction reaction in the CCR, with gas mixture (H2:N2) ratio of 1:4 at 875±5 °C for filling degree, fd , and reactor revolution, ω, ranging from 5.38 to 16.14 percent and 2 to 5 rpm, respectively. A creeping fluid flow condition (Re < 1) and natural heat convection (Gr/Re2 >> 1) were maintained during the solid–gas reaction, and the particle-bed behavior was quantified by Froude number for the optimum operating window. The simulation was validated with the experimental results of reactor reaction product by X-ray diffraction (XRD) and scanning electron microscope (SEM) images.

Coal bursts are one of the least understood yet the most critical hazards in underground coal mines. The ground motions induced by seismic events can trigger unstable failure of coal and rock mass and degrade the surroundings of an excavation. Therefore, the characteristics of ground motions should be fully investigated for an improved burst risk management. This paper analyzes ground motion features of a longwall panel from a typical underground burst-prone coal mine in China. The results showed that most of the ground motions on roadways were hardly initiate coal bursts due to insignificant energy input to the damage. The intensity of ground motions in near-field zone were nearly 20 times higher than those in far-field zone. The strongest vibration on roadway was induced by a coal burst with energy of 28,600 kJ, which can cause ground motion of 0.77 m/s and equivalent dynamic stress of 14.69 MPa. The findings of this paper can improve the assessment of seismic risks and its management.

Jan 7, 2020

By William Gleason

"In 2008, the world quietly hit a milestone that did not receive much fanfare or publicity, but it hit one that marked a turning point in the history of mankind and the way the planet is and will be inhabited in the future. It was in 2008 that, for the first time, more than half of the world’s population, an estimated 3.3 billion people, resided in urban areas. The world’s population had moved from being a majority of agricultural and rural society to an urban society. Andrew Whalley, deputy chairman for Grimshaw Architects, said this change in where and how people live will continue to increase urban populations and, by 2050, it is estimated that more than 6.4 billion people will live in urban areas. To meet these needs, Whalley, speaking during the keynote session of the 2105 Cutting Edge conference in Denver, CO, said future cities will have to be reimagined and redesigned to be more efficient. A large part of that design will be in the infrastructure of those cities.At the Fourth Annual Cutting Edge Conference, Sept. 21-23, much of the discussion was around how the tunneling and underground construction industries improve cities in a number of ways, including societal, environmental and in overall efficiency. There was talk, not just about the improvements that society enjoys at the completion of such projects, but also about the challenges faced by the owner and contractor in the construction of such projects.The conference, titled Urban Tunneling, brought together some of the top minds in the industry to not only discuss the issues faced today, but also those that will shape the industry in the future.For his part, Whalley spoke about a number of projects around the world and how they have impacted society in ways beyond simply providing a better means for transportation of people or water. Notably, he spoke about the Crossrails project in London.London is a city of 8.6 million people and a history that dates back nearly 2,000 years. It is a great example of the challenges the industry faces in bringing modern efficiencies to an established city.Running more than 100 km (62 miles) with more than 42 km (26 miles) of tunnels passing through 40 stations, including 10 new stations, the project is the largest in Europe and will transform the way people move about the city."

Jan 1, 2015

By I. J. Dowdeswell

Perspective Man is a model maker. Throughout recorded history man has-used models both to provide insights into the workings of the processes which surround him and as a step towards the eventual control of those processes. These models have covered the field from extremely large systems (solar and celestial. models) to infinitesimally small systems (sub-atomic .and atomic models). Models have been developed for social systems, ecological systems, biological systems and economic systems: all fields of human endeavour contain the fruits of this restless model-making. The Role of Models Since the evidence of mans&apos; industry in formulating models is so abundant, it is worthwhile stating some of the reasons. Based on the simple definition that "a model is a convenient and useful representation of some facet of the &apos;real&apos; world", then a model provides a means for: 1. Understanding the thing being studied. 2. Communicating that understanding to others. 3. Manipulating the thing being modelled. The common denominator implicit in these reasons is that- improved control is the. objective off all modelling or simulation work. Improved control shows itself either directly by the development of devices which perform the control functions or indirectly by improvement in the decision making process itself. For example, in a process plant, a suitable model of part of the process could lead either to the use of automatic control devices such as set-point controllers or to the implementation of instructions (pre-defined decisions) which permit the operator to better control the process. Typical process control systems use both of these since fully automatic control is restricted to processes where the required information can be effectively measured.

Jan 1, 1972

Incremental sampling is defined as a solution to fight segregation, the theory is demonstrated and theoretical and practical aspects are discussed. The number of increments necessary for successful sampling is discussed. As an application, riffle splitter division is reviewed.

Mar 1, 2010

By James R. Hein

Barite and Fe-Mn-oxide deposits that occur along faults in the Southern California Borderland formed by low-temperature hydrothermal processes. The Borderland region consists of block-faulted continental crust within the broad transform boundary of the North American plate. The fault-bounded basins are anoxic and partially filled with hemipelagic and turbidite sediments. Barite was collected from four dredges and a submersible dive (DSV4-355) in the southern California Borderland, and was collected from two sea-cliff sites along the Palos Verdes Headlands near Los Angeles. Barite at these seven locations occurs along strike-slip and basin-margin faults from the shoreline to 1800 m water depth. Submersible observations showed a series of mounds up to 10-m high composed of friable, white barite associated with diffusely venting milky fluid; the mounds support large benthic colonies, including tube worms (Lonsdale, 1979). Barite samples recovered from dredges are brown, green, and white and range from porous, vuggy fragments to massive fragments cut by banded barite veins. Samples from two dredge sites contain fossil worm tubes 1-3 mm in diameter and >10 cm long. All the samples are nearly pure barite, with only minor to trace amounts of other minerals. Chemical analyses show 94-98 wt. % BaSO4, low total rare-earth element (REE) contents (<45 ppm), Sr contents from <2 to 10,000 ppm, and Hg contents up to 1 ppm. Chondrite and shale-normalized REE patterns show light REE enrichments and large positive Eu anomalies. These REE pattern characteristics are typical of marine hydrothermal fluids and minerals. Sulfur isotope ratios (d34SCTD) from +21.6 to +67.4? range from seawater values (+21?) to exceptionally high positive values. Strontium isotope ratios are lower than the modern seawater ratio as well as the seawater ratio that existed at the time of deposition of the host rocks.

Jan 1, 2002

By Don Rose

In the USA the cost of steel ribs for tunnels approximates $100 million each year. European practice has long since abandoned heavy steel ribs for tunnel support, and tunnel coats in Europe (normalized for wages) are about half the costs incurred in the USA. A feeling has existed for some time that the USA practices of supporting tunnels with heavy steel ribs have been overly conservative. The USA practice is based on rock load coefficients by Karl Terzaghi. In 1946, Karl Terzaghi published a tunnel rock classification system (Terzaghi, 1946), with the rock loads on tunnels predicted for each class of rock. No data on real rock loads were presented by Terzaghi and his rock load coefficients may have been largely intuitive. His classification system and associated predicted rock loads have been widely used in the USA. Each rock class, taken from Terzaghi&apos;s classification system, is assumed to generate loads of loosened rock resting as dead load. The dimensions of the loosened rock are described by rock load coefficients multiplied by the tunnel diameter. The resulting rock loads are used by design engineers, contractors and agencies to size supporting steel ribs. Terzaghi clearly stated that he had conservatively assumed high rock loads for his classes 4, 5 and 6 to take a presumed effect of groundwater into account. If the tunnel was not affected by ground- water, Terzaghi stated those rock loads should be reduced by 50 percent. Twenty two years later Tor Brekke (1968) wrote a paper clearly showing that based on observation of more than 250 tunnels groundwater does not affect tunnel rock loads. In 1969, Deere, et al., published measurements made on a number of tunnels, and a well-known curve was drawn by Deere to illustrate Terzaghios coefficients graphically. Deere&apos;s text stated that Terzaghi&apos;s predicted rock loads were too high and should be reduced. Cording and Deere (1972) more recently published data indicating that very large real rock caverns and chambers were being successfully built using rock bolts, which can take only a very limited rock load, thus indicating that real rock load is much smaller than Terzaghi or even Deere predicted.

Jan 1, 1982

By Bradley Stoughton

A LL over our great country I have been privileged to see, during the last six weeks, the manifestation of a new spirit among engineers. Partly under the inspiration of leaders whose influence has been felt not only nationally, but internationally, - partly through the recognition of the service that engineers have been able to render to the nation during the recent crisis, a new self-consciousness has been acquired by the individuals, and now this self-consciousness seeks expression in opportunities for service and participation in public affairs. The engineer . no longer sees himself a mere reservoir of information to be tapped when some one is in need of cold facts, no. more an administrator of mere material things, but a potential administrator of- public affairs, a citizen and a human being, with the responsibilities, as well as the privileges of citizenship.

Jan 1, 1920

By H. W. Kasaini, E. Bourricaudy, T. Larochelle

Rare Element Resources Inc., a U.S. based company, has developed a three-stage process for producing a +98% mixed REO powder from hard rock feedstock (-48 mesh, 2.9-4.8% REO) consisting of bastnaesite and ancylite minerals. Firstly, the whole ore is digested in chloride media at low temperature in counter-current flow mode. Secondly, the rare earths (REEs) are selectively precipitated as oxalates directly from an impure pregnant leach solution (PLS). Finally, significant amounts of free acid and water are recovered from the REE-depleted filtrate and subsequently recycled within the process. Excess heat from the oxalate calcination process is captured and reused in the plant. Due to the low leach temperature (45 ºC) and moderate acid dosage (240-297 kg/t, HCl), rare earth oxides (REOs) are preferentially leached out of fine solids leaving most of the base metals (Ba, Fe, and Al ) in the residue. Selective recovery of REEs from the PLS is achieved by mixing dilute oxalic acid (33% H2C2O4) and PLS at elevated temperature (85-95 ºC). The REEs plus thorium are precipitated as oxalates (REE2 (C2O4).xH2O) while the base metals are left behind in the barren filtrate. Multiple batch and pilot test results have confirmed that 50-80% of the oxalic acid can be recovered from the REE-depleted PLS through low-temperature crystallization (10-15 ºC). Typical leach efficiencies of critical rare earths at 45 ºC range from 85-99% (average 93%) while oxalate precipitation at high temperature increases the crystal size of RE oxalates (>450 microns, d80) thereby improving filtration. The economic benefits of this process include elimination of flotation and magnetic separation Capex and driving hydrometallurgical Opex down to $6- 7/kg, REO produced. As part of a comprehensive risk mitigation strategy, Rare Element Resources Inc has operated multiple pilot plants at SGS in Lakefield, Ontario, Canada to optimize counter-current leaching (CCL), REE oxalate precipitation (OXP), and thorium removal circuits. This paper presents pilot testing data from CCL and REE OXP circuits.

Jan 1, 2016

By V. Yahorava

Resin-in-pulp (RIP) technology has recently often been considered for the direct recovery of base metals and uranium from dense pulps. Implementation of RIP will eliminate the requirement for any solid-liquid separation downstream of leaching and has the potential to combine the recovery and purification steps, hence reducing both capital and operating costs. The recovery of the valuable metal is expected to be higher when RIP is used, especially where the leached solids are difficult to settle or filter, and to wash. The main concerns about the use of RIP for uranium recovery from dense pulps are the impact of silica on the resin?s metallurgical performance and the operating costs that would be associated with resin loss. Although a number of resin manufacturers have been developing much improved RIP-grade resins, it is critical that the most cost-effective resin be selected. Mintek currently is doing a significant amount of work on silica fouling of RIP-grade strong-base resins in acidic leach liquors and the effect it has on the performance of the resin, including its durability. This paper describes the results of the test work done on silica fouling and its impact on plant design input data. Resin durability test work was done using various laboratory techniques, but durability was also evaluated on a relatively large scale using actual pumps, screens, and mechanical agitation. Based on the results generated, a preliminary economical evaluation was done to estimate the impact of resin loss on the overall economic viability of a specific application. Keywords: resin-in-pulp, silica fouling, resin loss, equilibrium, kinetics, elution, durability, mechanical strength, resistance to attrition.

Jan 1, 2009

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na&apos; and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°&apos;K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°&apos;K and

Jan 1, 1968