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By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963

By L. W. Higley

Procedures were developed for reclaiming high-temperature alloy scrap in the form of standard cobalt-base alloy. A cobalt-base, multicomponent, high- temperature alloy, such as S-816, can be successfully melted from scrap, and its specified chemical composition can be retained. Induction furnace melting in a controlled atmosphere was used to obtain ingots that were subsequently fabricated by impact forging to provide specimens for heat treatment and testing. Of the numerous metal elements in S-816 alloy, only small quantities of molybdenum were lost in the melting operation as finally developed. Test results indicated that the scrap material, after melting, forging, and heat treatment, was equivalent in room-temperature tensile strength, in high-temperature creep and stress-rupture properties, and in chemical composition to commercially produced S-816 alloy made from virgin material.

Jan 1, 1963

By W. W. Agey

Past investigations on waterborne impurities in the flotation process have been concerned primarily with the treatment of specific ores with particular local waters. Although some anions and cations present in water are known to react with flotation reagents, a definitive study has not been made on the effect of such common ions upon the flotation process. This report describes the fundamental research undertaken to define and measure the adverse and/or beneficial effects of different concentrations and combinations of several common anions and cations when oleic acid is used to froth-float limestone from a pulp of quartz and limestone. Research on the effect of waterborne impurities upon the flotation process was composed of two equally important phases. The first phase comprised development of a procedure for floating limestone from quartz that would give the same results in test after test. Some difficulty was encountered, but once such a procedure was developed, the second phase, comprising study and measurement of the effect of various ions c on to natural water upon the flotation of limestone, was quickly completed.

Jan 1, 1963

By A. J. Paul Laprairie

The process for which it is to be used is too often the only consideration in the design of a vessel. A de-sign allowing for practical manufacture and erection, as well as for proper maintenance, can often give over-all economies. Most platework in-stalled today is of welded construction. Therefore, metallurgical control is important in its manufacture. Also, because many concentrating and re-fining processes tend to be corrosive, the subject of protective coatings as a part of the manufacturing process is extremely important. The plant de-signer should know how to evaluate and specify controls for the metallurgy and for the coatings. Mining operations are becoming more sophisticated in the field of mechanical engineering. More and more emphasis is being given to preventive maintenance. The first step in any maintenance program, however, is good inspection service. This paper will suggest methods for the inspection of platework, and outline methods for repair and replacement.

Jan 1, 1963

By P. R. Tisot

Knowledge acquired from this research contributes to a better understanding of the physical structure of Green River oil shale and provides fundamental data and concepts that may serve to improve oil-shale technology. This study by the Bureau of Mines indicates that oil shale is a highly consolidated organic-inorganic system with no significant micropore structure, pore volume, or internal surface. This system is a form of physical structure that precludes rapid diffusion of either gases or liquids. The mineral matter consists essentially of nonspherical particles that tend to follow a log-normal size distribution. An excess of 99 weight-percent of these particles have equivalent spherical diameters of less than 44 microns--75 weight-percent are from 2 to 20 microns, and 15 weight-percent are less than 2 microns. The surface area (3 to 5 square meters per gram) of these mineral constituents is mainly external surface. The mineral constituents contain some micropore structure--pore radii ranging from 10 to 100 Angstrom--with the pore sizes randomly distributed. Distribution of the organic matter within the inorganic matrix is essentially interparticle and not intraparticle. The organic matter within the micropores of the mineral constituents is less than 4 percent of the total. Estimates made from surface area data suggest that perhaps only a small amount of the organic matter is bonded either physically or chemically to the mineral constituents.

Jan 1, 1963

The properties required for a com-pound to form useful thermoelectric materials are described. Uranium compounds which might have these properties are reviewed. Several of these compounds have been prepared and fabricated into compacts. The apparatus used for hot pressing, and for the measurement of thermoelectric power, electrical conductivity and thermal conductivity, is described. Detailed attention has been given to the properties of the nitrides. Preliminary studies on a number of other uranium compounds are reported. The figures of merit of the best materials so far examined are one-tenth of those necessary for a useful thermo-electric material. THE efficiency of thermoelectric materials for power generation and cooling is determined by their figure of merit, Z = a2 a/K, where a, a and K are thermoelectric power, electrical conductivity and thermal conductivity, respectively. It is well known that the largest values of Z are achieved with semiconductors (1). High mobility of charge carriers is necessary for simultaneously high thermoelectric power and electrical conductivity.The properties required for a com-pound to form useful thermoelectric materials are described. Uranium compounds which might have these properties are reviewed. Several of these compounds have been prepared and fabricated into compacts. The apparatus used for hot pressing, and for the measurement of thermoelectric power, electrical conductivity and thermal conductivity, is described. Detailed attention has been given to the properties of the nitrides. Preliminary studies on a number of other uranium compounds are reported. The figures of merit of the best materials so far examined are one-tenth of those necessary for a useful thermo-electric material. THE efficiency of thermoelectric materials for power generation and cooling is determined by their figure of merit, Z = a2 a/K, where a, a and K are thermoelectric power, electrical conductivity and thermal conductivity, respectively. It is well known that the largest values of Z are achieved with semiconductors (1). High mobility of charge carriers is necessary for simultaneously high thermoelectric power and electrical conductivity.

Jan 1, 1963

By R. E. Smallman

R. E. Smallman (University of Birmingham, England)—Recently, Tedmon and Ferriss11 have determined the yield stress parameters oi and ky for tantalum by measuring the lower yield stress as a function of grain size 2d and fitting the results to a relationship of the form They report that although ky , which is taken to be a measure of the dislocation locking strength, is small (- 2 to 4 x 106 cgs units) a substantial yield drop is nevertheless observed in a normal tensile test. Niobium gives a similar result,12-14 as pointed out in the original work by Adams et a1.,12 and in order to check this apparent anomaly the yield-stress parameters of electron beam-melted niobium have recently been reanalyzed15 by the Luders strain technique. In this method the strain hardening part of the stress-strain curve is extrapolated to zero plastic strain; the intercept on the preyield portion of the curve is taken to give oi, whilst the difference between oi and the lower yield stress gives kyd-1/2. The results indicate that ky increases with increasing grain size and hence, a plot of vs d-112 yields an apparent ky, which is lower than the true value. A similar effect could account for the small ky found in the relatively pure tantalum used by Tedmon and Ferriss. The variation of ky with grain size shows that dislocations are more strongly locked in coarse-grained specimens than in fine-grained samples. In niobium, this may be attributed to the fact that the dislocation density in the fine-grained material is higher than that found in the coarse-grained samples which are given a sufficiently prolonged anneal to remove any residual substructure and, since the metal contains only a small amount of interstitual impurity, a variation in locking occurs. By contrast, application of both the grain size analysis and the Luders strain method to yield-stress data from commercially pure vanadium containing a large amount of interstitial impurity gives consistent values of oi and ky, with ky independent of grain size and temperature. Electron microscope observations show minor variations in dislocation density from grain size to grain size, but in any case in this material the dislocations are heavily locked with precipitate. On yielding new dislocations are generated and, as a consequence, the importance of any differences in dislocation density between the various specimens of different grain size is considerably reduced. It is perhaps significant that Adams and lannucci,16 working with a grade of tantalum containing a higher interstitial content than that used by Tedmon and Ferriss, prepared the specimens of different grain size by annealing in the temperature range 1500" to 2000° C to minimize any differences in dislocation structure, and found that ky had a value of 1.04 x 107 cgs units, independent of testing temperature. Such behavior is consistent with the dislocations being locked by carbide precipitates so that the generation of free dislocations is an athermal process. The recent work of Gilbert et al.17 also shows that in tantalum there is no significant variation of ky with grain size provided it contains 150 ppm of oxygen. In this case, however, the dislocations are not locked by precipitate and ky is temperature dependent. C. S. Tedmon and D. P. Ferriss (authors' reply)— We would like to thank Dr. Smallman for his interesting comments and discussion to our paper, "The Dependence of Yield Stress on Grain Size for Tantalum and a 10 pct W-90 pct Ta Alloy".18 It was suggested that perhaps the relatively small values obtained by us for ky of tantalum could be attributed to the same cause that accounts for the apparently small values of ky that result when it is determined by the Luders Strain technique. Since our values were obtained by plotting the lower yield stress vs the reciprocal of the square root of the grain size, it is not clear how this could be the case. The values of ky in this experiment have been calculated, using the Luders strain technique. With this method, values for ky on the order of 2 x 105 to 5 x lo6 cgs units were obtained. In spite of this rather large variation, the magnitudes are still small, and there appeared to be no good correlation between ky and the grain size or the yield stress, probably because of the difficulty in accurately extrapolating the work-hardening portion of the curve back to zero plastic strain. As was shown in the original data,18 there was little work hardening in any of the curves, at any temperature. In his discussion, Dr. Smallman also points out how ky has been observed to increase with increasing grain size, when determined by the Luders strain technique. There are at least two possible explanations for this. In the first case, if it is assumed that the bulk of the interstitial impurities are concentrated at the grain boundaries, then, of course, the available grain boundary area would decrease with increasing grain size, thus presenting less area for the interstitials, which would then presumably increase the concentration within the grains, thereby increasing the locking of the dislocations. In the second case, the increase in ky with increasing grain size would be attributed to the nature of the grain boundary itself. One of the several ways of deriving the Hall-Petch equation19 is based on the stress concentration arising from a pile-up of dislocations at the boundary. The ability of the stress concentration to unlock a source in a neighboring grain would depend on the strength of the grain boundary. As is well-known, the nature and struc-

Jan 1, 1963

By R. Barany

The heats of formation of gehlenite and talc were determined by hydro-fluoric acid solution calorimetry. The results are reported in terms of the constituent oxides (?H298.15 = -31.1 ± 0.5 kcal/mole for gehlenite and ?H298.15 = -44.9 ± 0.3 kcal/mole for talc) and in terms of the constituent elements (?H298.15 = -952.8 ± 0.7 kcal/mole for gehlenite and ?H298.15 -1,415.5 ± 1.4 kcal/mole for talc).

Jan 1, 1963

By T S. Cochrane

A variety of practical tests have been tried in the mining industry to determine the support properties of mine roof bolts. Such tests include torsion wrench readings, hammer blow tests and the use of plates with built-in tension indicators. This paper gives some details of pull tests with a hydraulic jack, as carried out in coal mines of western Canada. M A~Y criteria exist for establishing the efficiency of roof bolting, and the one adopted de-pends on the nature of the problem and on the individual leanings of the investigators. Consequently, sufficient studies have not been made from a common viewpoint or under similar geological and techno-logical conditions to compare these methods of evaluation. However, regardless of whether certain tests provide sufficient factual data to form a basis for theoretical research on bolting or not, many of these tests can and do provide a positive means of judging the suitability of chosen roof bolting techniques and equipment under definite geological conditions.

Jan 1, 1963

By M. B. Mirza, F. D. Wright

Models of photoelastic material were made to simulate a mine roof that had cracked over the edge of the pillars and at the center of the span. Models were restrained from moving laterally outward so they acted as flat arches. Uniform loading was approximated by loading the models along the bottom at eight points spaced equally along the span. It was found that for models with depth to span ratios of 1:3 to 1:6, the maximum stress at the top of the center crack could be calculated directly by the following formula: Elastic stresses in mine roofs composed of sedimentary beds are usually computed by assuming that the immediate roof bed acts as a fully restrained beam uniformly loaded by its own weight and by overlying strata. Very little work has been done to analyze stresses in roof beds or beams which contain vertical (normal to the span) or nearly vertical cracks. Yet every mining engineer has walked safely under roofs that show such cracks. As far back as 1933, Bucky' made model studies of the effect of vertical cracks on the behavior of horizontal strata. He did not make any analysis of the stresses but did show that a cracked beam will stand safely under certain conditions, and also showed that a beam restrained at the ends can crack over the supports and in the middle without collapsing as long as the ends of the beam are not free to move laterally outward. The beam, or rather, part of the beam, acts like a flat arch and supports itself by pushing outward at its supports. In 1941 Evans2 treated analytically the problem of a beam cracked along so many planes perpendicular to the axis of the beam that no tensile stress can operate. He named this type of beam a "voussoir-beam" by analogy to the voussoir-arch. In 1962 ~a~cocks~ modified Evans's solution by including the effect of the shear stress component of the resultant force at the abutment. This paper gives the results of a photoelastic study of the stresses in a beam containing vertical cracks in the center of the span and over the supports. A

Jan 1, 1963

By L. G. Marshall

This report presents a cross section of the sand and gravel operations in the Minneapolis-St. Paul area. The study covers individual operations, economic problems peculiar to the industry, glacial geology of the area and its effect upon the grades and types of products, and past, present, and future trends of the expanding population and its effect upon the industry.

Jan 1, 1963

By J. B. Clark, A. J. McEvily, R. L. Snyder

The nonuniform distribution of precipitate particles has been recognized as a leading factor contributing to the relatively low fatigue resistance of aluminum alloys. The structure of many of these alloys is characterized by narrow precipitate-free zones adjacent to the grain boundaries. Alloys with such zones exhibit a tendency for brittle inter crystalline fracture. The interrelation between this type of structure and mechanical properties was investigated in an Al-10 wt pct Mg alloy. It was found that deformation during fatigue occurs preferentially along these zones and cracks initiate there. In Al-10wt pct Mg, the zones were found to be supersaturated even after extensive general precipitation and are due to the absence of proper precipitate nuclei in the region near the grain boundaries. Cold working the alloy prior to aging improves the mechanical properties by inducing precipitation within the zones and also by jogging of grain boundaries. The mode of fracture is changed from brittle inter crystalline to more ductile trans granular fracture. THE process of fatigue is highly structure sensitive, with the strength of the whole often dependent upon some localized discontinuity, either geometrical or metallurgical in nature. Much has been learned about the role of geometrical discontinuities, e.g., notches, in fatigue, but with the exception of the effects of inclusions or the shapes of carbides, relatively little is known about the specific effects of discontinuities in metallurgical structure such as nonuniform precipitation. In most age-hardening aluminum alloys, metallo-graphic studies have shown that the extent of precipitation adjacent to grain boundaries is much less than that which occurs in the interior of the grains. The width of these almost precipitate-free regions, which are sometimes called denuded zones, and the extent of solute depletion within them, are dependent upon the particular alloy and its aging treatment. It has been observed1 that these zones are relatively soft with the result that plastic deformation takes place preferentially within them. It has also been shown 2-4 that there exists a tendency for intercrys- talline cracking in fatigue when such zones are present. It is of interest to note that Broom et al.2,3 were able to reduce the incidence of this type of failure in an A1-4 wt pct Cu alloy by stretching the material 10 pct prior to aging. In the present study, the effects of precipitate-free regions on the fatigue properties of an A1-10 wt pct Mg alloy were studied in detail, and the effects of deformation prior to aging on the nature of the precipitation process as well as on fatigue properties were also investigated. MATERIAL AND PROCESSING An A1-10 wt pct Mg alloy was selected for this study, because it was known that well-defined precipitate-free regions along the grain boundaries are readily obtained in this alloy after aging at 200oC.5 The starting materials were 99.998 pct A1 and singly sublimed magnesium of about 99.9 pct purity. The aluminum was induction melted in a graphite crucible, and then the magnesium addition was immersed until dissolved. Chlorine gas was then bubbled through the molten alloy for 4 min to degas the melt, after which the melt was cast at a pouring temperature of 730" to 760°C into a cold, graphite-coated, tapered steel mold. Since A1-Mg alloys are difficult to homogenize,5 special care was taken to obtain a uniform composition. Two-in. cubes were cut from the ingot and heated at 446°C for 30 min. These cubes were then hot forged approximately 35 pct in each of the three cube directions and homogenized for 16 hr at 446°C. Sheet specimens were then obtained by pressing 40 pct and rolling 35 pct per pass with reheating between reduction steps to a final thickness of approximately 0.10 in. The sheet was then solution treated for 16 hr at 446°C and water quenched. The age hardening behavior of this material at 200°C was then determined, and the results are shown in Fig. 1. The age hardening of this alloy when subjected to cold work prior to aging is also shown in this figure. Preliminary work indicated that extensive deformation after quenching was required to affect drastically the precipitate-free regions in this alloy, and a rolling reduction of 50 pct was chosen. For purposes of comparison the following three conditions were studied: a) Solution treated, quenched, and aged 20 hr at 200°C

Jan 1, 1963

By T. G. Lovering

Nonparametric statistical tests have practical application to many geological problems because, unlike the standard statistical tests, they do not require assumptions regarding the form of the population frequency distribution. Many of them do not even require that the variable be susceptible to numerical measurement. These tests are useful either 1) for geological data representing population distributions of unknown form, or otherwise not meeting the requirements for standard parametric tests; or 2) for sample attributes that cannot be measured but only ranked in order of relative magnitude. The application of two such tests will be illustrated. The Kolmogorov-Smimov test will be used to test for significant differences in copper distribution in samples of two rock types; the Spearman rank-correlation method will be used to determine whether there is a significant association between intensity of rock alteration and copper content of the rock. Nonparametric tests are, in general, quicker and easier to perform than the corresponding parametric tests, and they may be applied to a greater variety of data. They are not as powerful as the standard tests if used on data to which the latter are applicable, and computer programs utilizing them are not generally available. The use of standard or parametric statistical procedures for the interpretation of measured geological data is familiar to most mining engineers and explora- tion geologists. The computation of product moment correlation coefficients on sample assays for more-than one component is already standard procedure in some company operations, as is the use of Student's F test and Snedecor's F test for the comparison of means and variances of sample groups. The application of these three tests is limited by the prerequisites that the samples must be random, independent representatives of normally distributed populations and that the variables involved must be measurable. If such tests are applied to data which fall short of fulfilling these prerequisites, then the probability level attributed to the computed statistic is invalid and the conclusions based thereon may be erroneous. A number of nonparametric, or distribution free, statistical tests have been developed for use with data which are not amenable to standard parametric procedures. These tests have been widely used in the behavioral sciences such as psychology and sociology for some time, but their application to geologic problems is relatively new. Nonparametric tests may be grouped into two main categories: those which test for significant differences in a single variable by comparing either sample values with a standard value or representative values between two or more groups of samples; and those which test for significant association between pairs of variables in a single group of samples. The versatile chi square test, the Kolmogorov-Smirnov one and two sample tests, the Wilcox matched pairs signed ranks test, the median test, the Mann-Whitney U test and the Cochran Q test are examples of nonparametric tests with demonstrated or potential geological applications that belong in the first category. The contingency coefficient, Spearman rank correlation coefficient, Kendall rank correlation coefficient and the

Jan 1, 1963

By G M. Thorpe

This paper discusses mine research at Inco, giving specific examples of research projects which illustrate the approach to mining problems. The first example covers the development of a new mining method, "undercut and fill," which was originated for mining badly broken-up pillars, but which is now rapidly replacing the square set method of pillar recovery. In the new method, ore is extracted in a series of successive horizontal cuts, progressing downward, a cut being completely mined and filled before the cut below is started. In the second example, improvements to the "cut and fill" method of mining are discussed. These improvements are the result of improved techniques and improved equipment, etc., with, in many cases, the former being made possible by the latter. The advances made have permitted the use of the "cut and fill" method at much greater depths than before. The third example is presented to illustrate research undertaken to obtain the earliest maximum advantage of the introduction of a new piece of equipment or material. For this purpose, the development of the "Under-ground use of AN /FO Blasting Agent " has been selected. Work on this project started in May, 1960, at a time when there was very little in-formation regarding the potentialities of AN /FO for underground blasting, either primary or secondary. By the end of 1961, AN /FO made up 64 per cent of the explosives used under-ground at Inco mines.

Jan 1, 1963

By F. G. Miller

It is generally accepted that sulfur exists in coal in three forms: (1) pyritic, (2) organic, and (3) sulfate sulfur. Sulfate sulfur usually makes up less than 1% of the total sulfur content. Pyritic and organic sulfur, make up almost all of the total sulfur and occur in varying amounts in different coals and can vary greatly in coal of the same seam Pyritic sulfurs of 20% to 80% of the total sulfur have been reported Other authors have shown that it is not possible to remove the organic sulfur without chemically altering the coal. Chapman and Jones (1) state: "Organic sulfur, unlike pyritic sulfur does not exist as discrete particles, but is intimately associated with the coal structure, and as such it is not possible to remove it or reduce its concentration by physical means." Any success in removing sulfur has come about by removing pyritic sulfur by physical means; therefore, removal of sulfur in the pyritic form is the subject of this investigation. The extent to which any impurities can be removed from a particular coal can be determined by a washability study. Outside of crushing coal, to finer sizes or chemically altering the coal, there are no known methods of changing this inherent washability characteristic. The efficiency of various methods used to remove impurities can be determined by comparison of results produced at a yield to the results as shown by a washability study. In recent years heavy media processes have proven their ability to wash plus 28 mesh coal and nearly produce results shown to be theoretically possible by the washability study. Therefore, it is the objective of this paper to show various methods of treating the finer fractions of the coal, in the hope of developing a process, which can effectively produce in the fine fractions the efficiency of heavy media devices in the coarse.

Jan 1, 1963

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By Lawrie DC

Finely ground beryl was decomposed by mixing with ground limestone and soda ash andheating at 900¦C for,4-6, hours.The sintered material was then crushed and leached by boiling under reflux with 5N sulphuric acid for up to 4 hours. The liquor containing Be, ; Al, . Fe and, other elements as sulphates, was separated from the residue which consisted mainly of silica and gypsum, either' by filtration or by decantation washing.The clarified leach liquor.was first treated to remove Fed}: , by contacting with a primary amine-kerosene solution in2 counter-current stages. The iron free liquor wa,s then passed to a 4-stage counter-current extraction unit where it was con-tacted with 0.5M di-(2 ethyl hexyl), phosphoric acid (EHPA) in kerosene. The'operating conditions were such that at least 99 p'br cent of the Be and only 7' per' cent of the Al- was, extracted The ,B6`= and. Al were ;stripped from the organic phase by sod-ium hydroxide solution of suitable concentration to form soluble "beryllate" and "aluminate" respectively. Most of the Be was subsequently precipTitated a's Bo(OH)2 by-hoating the alkaline solution to 90C, the Al remaining in solution. After filtra-tion and washing, the Bo(OH)2 could be ignited directly to BeO at about 1000 C or used as a feed to further purification stages aimed at producing "nuclear grade" BeO.A small coaAter-current extraction unit was operated con-tinuously using liquor derived from the sintering and leaching stages. Data obtained in batch laboratory tests were confirmed. A product obtained by ignition of the washed "beryllate" precip-itate contained more than'99 per cent BeO.

Jan 1, 1963

By J. J. Kramer, G. W. Wiener, K. Foster

The effects of the primary grain size and sheet thickness on the secondary growth rates of grains with (100) surface planes were studied in 3 pct Si-Fe sheets. This secondary grain growth was carried out under conditions in which the {100} plane had the lowest surface free energy. The value of the surface energy difference, between the (100) plane and the random matrix planes was found to he only about 3 pct of the grain boundary energy, indicating that most of the driving force for secondary growth is supplzed by grain boundary energy. A method for obtaining cube texture in 3 pct Si-Fe sheets by a secondary recrystallization process has been reported.' It has been demonstrated that a difference in surface free energy between the (100) plane and other planes is responsible for this growth, where the (100) plane has the lowest surface energy. A semiquantitative relation has been derived for secondary grain growth in sheets where primary grain growth has proceeded until the grains have grown through the sheet and the average grain diameter in the plane of the sheet is from one to two times the sheet thickness. Then, the linear growth rate, G, for the secondary grains can be given by where M is the grain boundary mobility, is the grain boundary free energy, is the average primary grain radius, A is the average difference in surface free energy between the (100) plane and planes of other orientations, t is the sheet thickness, and C is a term first proposed by zener6 which acts as a negative driving force, the effect of inclusions in holding up grain boundary motion. Since the problem of grain growth being discussed is under conditions where the matrix grain size is at least equal to the sheet thickness, the radius r is, of course, a function of the sheet thickness. The term B/r is the grain boundary driving force normally associated with inclusion inhibited or texture inhibited secondary recrystallization. Here, however, the term is modified to account for the fact that growth occurs in thin sheets. The term is the additional driving force available because of the difference in surface free energy. The purpose of the present work has been to evaluate the driving force terms of the growth equation by studying growth rates of (100) secondary grains as a function of sheet thickness and primary grain size. From these data it has been possible to determine the relative values of grain boundary energy, surface energy difference, and the inclusion term, C. EXPERIMENTAL PROCEDURE A 3 pct Si-Fe alloy was melted and cast under a helium atmosphere using electrolytic iron and a pure commercial grade of silicon as raw materials. The alloy was hot and cold rolled to a thickness of 0.6 mm, and samples approximately 5 in. long by 1 1/4 in. wide were cut from the cold-rolled sheets. Four different primary grain sizes were obtained

Jan 1, 1963

By H. W. Kilau

Thermodynamic calculations indicate that an electrochemical cell might serve as an analytical device for determining the composition of high-purity metals. An equation, readily derived, for the cell voltage, E, is as follows: [E I RT In F NFe unknown sample T of L NFe standard] The cell, however, must come to equilibrium, must be reversible, and must have no thermal effects or complicating side reactions whose magnitude is indeterminable. This Bureau of Mines investigation explores the feasibility of an electrochemical technique for the analysis of high-purity iron. Experiments were conducted using room-temperature aqueous cells and high-temperature molten salt cells. The room-temperature cells proved to be irreversible. The high-temperature cells utilizing FeCl2 and a eutectic mixture of KC1-LiCl were reversible, but did not attain a constant voltage necessary for analytical considerations.

Jan 1, 1963

By Robert S. Warfield

The Bureau of Mines investigated a geologically favorable area in the Beluga River coalfield in south-central Alaska to determine if there were sufficient minable coal reserves for onsite utilization to meet the projected thermal power needs of the Anchorage area. A program of diamond core drilling and sampling delimited a shallow saucerlike structure estimated to contain indicated reserves of more than 20 million tons of subbitminous coal in a seam over 50 feet thick that could be mined by opencut methods. A large sample of fresh coal was taken across the full width of the seam for washability studies. This sample, with 4 volume-percent of clay partings eliminated, contained 24.4 percent moisture and 16.8 percent ash and had a calorific value of 7,162 Btu per pound. The studies indicated that mechanical cleaning would be of doubtful value.

Jan 1, 1963