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By R. J. Charles, G. Agar

Experiments on single particles show that the amount of material created during impact that is finer than any chosen size is proportional to the energy of the impact. As the underlying principle of comminution, it might be stated that each unit of energy input to a given comminution system tends to add to the system an identical assembly of new particles and subtract an equivalent volume of larger particles. Thus, two of the consequences of the fact that each unit of energy tends to add identical assemblies of new particles to the system are: 1) on continued application of energy the total charge in any batch comminution system tends to assume the characteristics of this assembly, and 2) the process of comminution may be described by a relationship such as E = Ak-a. Recently Schuhmannl presented a theory of comminution which puts rational perspective on the extensive controversy surrounding most of the existent theories of comminution. With hindsight the origin of controversy can be ascribed to a relatively simple circumstance. In general, a progressive shift of a size distribution curve towards finer sizes is observed as energy is added to a comminution system. It is also observed that, with continued grinding, the size distribution curves usually change and appear to approach some constant shape. Inves-tigators generally felt that an appropriate method of relating and generalizing such data would be to consider the hypothetical case where particles in the system were uniformly subjected to comminution such that each of these particles, receiving its proportion of input energy, was transformed into a number of smaller particles of uniform size. Since the changes in shape of the size distribution curves during size reduction were clearly associated with the coarse particles in the system, it was also assumed that these changes accounted for little of the input energy and one could deal solely with the equilibrium shape towards which the size distribution curves tended. Although the unrealistic nature of the foregoing points of view was realized some justification was felt for such treatments since, in most cases, the resulting mathematical formulae could, by the adjustment of at most two parameters, satisfactorily describe experimental observation. Difficulties arose, however, in that the formulae required a specific influence of the feed size on the comminution process. In actual fact, the application of a feed size term in fitting experimental data was often found to be unnecessary or contrary to the above formulae. Secondarily, much discussion arose concerning the appropriate energy number that would relate the size change of one particle to the amount of comminution energy it received. As has been previously shown3 all the above theories that treat comminution as a continuous process of size reduction may be related to a proposition of the following form: dE = -Cfn [1] where dE is the increment of energy, dx is the size change, x is the particle size, and C and n are constants. It is now clear, as pointed out by Schuhmann, that Eq. 1 is inapplicable to comminution processes, since comminution cannot be considered other than as a discontinuous mixing process in which the overall size distribution of the product results from mixing, in various proportions, finished material with unfinished, and sometimes untouched, material. A striking illustration of this mixing phenomena may be obtained by comparing the size distributions of grinds in a typical batch ball mill with size distributions calculated on the basis of mixing various proportions of feed material with a ground material which obeys a power law size distribution relationship. Figs. la and lb illustrate such a comparison and the similarity of these figures indicates that mixing plays an important role in determining the overall shape of the product size distributions. Figs. la and lb illustrate, additionally, the underlying basis of the comminution theory presented by Schuhmann.' In the preliminary grinding of relatively close sized feed particles in a batch ball mill, one may visualize that, when a successful encounter of a ball with a feed particle occurs, then the particle undergoes severe size reduction and the size range in which the resultant particles reside is far removed from the size of the feed particles. After a number of feed particles are reduced by independent but similar impacts and one examines the size dis-

Jan 1, 1961

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956

By C. C. Harris

A critical literature review leads to a descriptive model of tumbling mill operation based upon energy partition concepts and the necessary requirements for particle fracture. As grinding proceeds into the ultra-fine region, conditions which are of little significance during normal operations gradually become controlling. These involve increasing resistance to fracture and an increasing tendency to aggregate as particles become smaller, and a growing fraction of the power input being consumed fruitlessly. The result is that fineness asymptotes to a maximum value as comminution proceeds indefinitely; thus where t is time, p and n are experimentally determined parameters, and Ø is a measure of fineness, which is presumed to be proportional to specific surface area, or proportional to the reciprocal of the size modulus (provided that the distribution modulus remains constant with time), or both. Ø, is the asymptotic value of Ø and is a measure of the grind limit. A method for its graphical determination is given. In a previous paper1 the physical and mathematical principles requisite to a study of the role of energy in comminution were reviewed. The micro-process of comminution — or the comminution event — can be investigated in terms of (a) the magnitude of the force-field localized around the individual particles which gives rise to the stresses generated in the particles, which in turn induces their fracture, and (b) the distribution of fragment sizes, should the event prove fruitful. The entire fragmentation operation can be considered to be the totality of its individual events, and in order to obtain a single independent variable of the process it is necessary to transform and sum the local stresses in terms of energy.1 This energy, however, will account for only a fraction of the energy input to the comminution process, the actual magnitude depending upon the kind of mill and several related factors. From the comminution viewpoint the primary function of a mill is that of stressing as many as possible of the individual particles of the charge to failure, with the maximum economy of energy expenditure. This is difficult indeed to achieve, for stressing a particle does not always break it, while the overwhelming portion of the energy input is involved with various internal mill processes which — almost incidentally — determine the magnitude, frequency, and manner in which the forces are applied to the particles. Essentially, these processes depend upon the mill dimensions, loading and speed, and they may be little affected whether fracture occurs or not. These processes must be delineated if a complete description of the role of energy in comminution is to be given; the energy account sheet1 (Fig. 1) in showing how the energy is partitioned for the requirements of the several functions it performs, provides a framework for the development of a model of the comminution process. Actual numerical values for the variables appearing in Fig. 1 will depend upon the mill, materials, and operating conditions. A possible general relationship between the variables will be suggested in this paper. Before proceeding further, a cautionary note must be issued. It was pointed out in an earlier paper' that while energy input is not changed by increasing the power and decreasing the time in the same proportion, and vice versa, the results of the process in terms of particle fineness may be different. Thus, although energy is chosen as the independent variable of a comminution process, it is not absolutely independent, and care must be exercised to ensure that it is used within its range of valid application. Time has the necessary independence, and it will be used in place of energy where it is appropriate. The residence time in a mill is usually of the order of minutes. Under these conditions the particles are subjected to "... a relatively constant fracture producing environment".2 However, under the more rigorous conditions of greatly extended time, which pertain in ultra-fine grinding, indications are that the fracture producing environment no longer remains constant; this is the major subject of this paper. At this extreme limit the mill is probably taxed to its utmost, and at the same time the bulk material properties are becoming closer to ideal, while the physico chemical effects associated with surfaces, edges and corners are multiplying. (The edge length per unit volume is proportional to the square of the specific

Jan 1, 1968

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.'.' In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes' upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies' is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

By J. G. Balkestein, J. W. R. Baerts

During an attempt to develop a method for accurate, rapid, continuous analysis of ash content of wal, the Dutch State Mines Laboratory found that the absorption coefficient for X-rays was related to ash content. This relationship was utilized in the development of an apparatus called CendreX, used to measure the absorption and in turn the ash content. The principle, procedure, accuracy, and applications of the CendreX automatic determination of ash in coal are discussed in detail. Until recent years coal preparation research was concentrated on the possibilities and efficiency of preparation equipment. Ever increasing demands for quality in coal, however, have caused researchers to become concerned with quality control. One of the characteristics strongly influencing quality (calorific value) and, consequently, the price of coal is ash content. Both customer and producer require that the ash content be controlled. To make this possible it is necessary for the producer to collect samples from the coal stream in the washery and to determine their ash content. On the strength of the results obtained the production process can then be adjusted, if required. Until recently incineration was the only method for determining ash content. When coal is incinerated with oxygen, it takes at least 15 min to determine the ash content. Even then some time may be lost in passing on the data. Therefore, this discontinuous and time-consuming method does not make a suitable starting point for checking, re-adjusting, or modifying the production process. Since it was not possible to accelerate incineration by mechanization and automation, another type of rapid continuous analysis had to be found. This would have to depend on some coal characteristic closely linked with ash content. At the Central Laboratory of Dutch State Mines, Dijkstra and Sieswerda found that the absorption coefficient for X-rays was suitable for this purpose. An apparatus based on the measurement of this characteristic was developed. Named CendreX,* this patented equip- *A Stamicarbon N. V. registered trademark. ment, used in combination with a sampler and conditioning apparatus, permits continuous determination of ash content with satisfactory exactness to within 3 min.t At the American Mining Congress meeting of May 1961, Log A. Updegraff, surveying aspects of continuous analyaia, reported on the CendreX appartus (Mining Congress Journal, August 1961). Since the first Condition for correct ash determination, whatever the method used, is always a sample taken in the right way, some practical aspects of sampling will be discussed first. SAMPLING In coal handling operations, each grain has its characteristic properties. In both the cross-sectional and longitudinal direction of the product stream the mixture of these grains is imperfectly blended. The elimination of the factor of segregation between the cross-sections from the direction of the stream is the principal aim of continuous analysis. Therefore, the samples to be analyzed are withdrawn in various places from the segregated product stream in such a way that they form a semi-continuous flow. In order to be truly representative of the product stream, the sample flow must fulfil two conditions: 1) The sample flow must be sufficiently large to insure that adventitious differences between the composition of the product stream and sample flow will be as small as possible. 2) All grains through the entire cross section of the product stream must have an equal chance to get into the sample flow. Since there is always a segregation through the cross section the sample flow will have a bias if the sampler collects only part of this section. In order to prevent the volume of the sample flow from becoming too large, the cross sections are taken discontinuously. However, this discontinuity gives rise to the adventitious differences that arise between the composition of product stream and the sample flow, and these differences become greater and are more deranging as the fluctuations follow each other more quickly. Moreover, the intervals between the morrnents of sampling mean a delay in the analysis. The aim will, therefore, be to collect small samples, or in other words thin cross-sectional increments, taken at sufficiently high frequencies. The following points should also be taken into account: 1) The smallest dimension of the openings in the sample collector must be equivalent to at least 3 d in

Jan 1, 1962

By N. J. Grant, D. S. Bloom

N recent reports, Sully' and Beck and coworkers' I have advanced hypotheses concerning the formation of the phase. Both of these hypotheses are based on Pauling's theories of the electronic configuration of the elements of the first transition group. Sully considered that the number of electrons which can be absorbed in filling electron "holes" is the factor which determines whether or not the structure can form. Beck suggested that the presence of a certain concentration of electron "holes" is the controlling value. It can be shown that a similar criterion can be developed without making reference to Pauling's theories. Table I shows the elements of the first transition group and the incidence of the a structure in the binary systems of these elements according to the data presently available. Also appended is the number of electrons considered to exist in the 3d-4s levels of these elements. If the atomic percentages for the phase are listed as shown in Table 11, and if the number of electrons in the 3d-4s levels per atom is calculated for the a boundary values, the results are as shown in the last column. It can be seen that the numerical values are all in the vicinity of 7 electrons per atom. This is true also for the ternary Cr-Mo-Ni IT phase, which occurs in a system in which none of the binary compositions are known to develop the phase. In the Fe-Mo binary, the high temperature a phase, which occurs at a composition of 50 atomic pct of each element, also yields a ,;1 e of 7 electrons per atom. From inspection of Tables I and 11, it develops that any series of sequential numbers which is assigned to the elements under consideration will result in the numbers pertaining to a compositions grouping themselves around one specific number. It does not follow, however, that this random number necessarily has physical significance. Such a point has already been discussed by Hume-Rothery." One interesting point develops from this study, however, and that is the position of manganese with reference to the other elements and to the phase. In the system used here, the formation of phase is associated approximately with the value of 7 electrons per atom, which is also the number of electrons per atom that manganese has. Manganese, it will be recalled, exists in three different crystal forms, none of which are the usual, simpler metallic forms; on the other hand, elements just to the left of manganese (in Table I) generally have lower coordination-number structures (body-centered cubic) than do elements to the right of manganese (face-centered cubic). The contribution to a complex crystal structure by the interalloying of elements from opposite sides of manganese is significant in that the a phase is formed in binary systems including one element from each side of manganese, with manganese capable of participating with both sides. It is indeed an interesting coincidence that manganese, with 7 electrons per atom, solidifies in complex crystal forms, and that when alloys of the transition elements are made which have seven 3d-4s electrons per atom, they, too, tend to assume a complex crystal form. From the above, it might be deduced that the study of the a phase might be advanced by a critical examination of the element manganese and how its structure is affected by small additions of elements which change the 3d-4s electrons per atom number. The role of atom size would also be of interest in formation. References ' A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, Part 4, p. 173. 2 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951). "W. Hume-Rothery, H. M. Irving, and R. J. P. Williams: The Valencies of the Transition Elements in the Metallic State. Proc. Royal Soc. (September 1951) 208A. p. 431.

Jan 1, 1954

By Charles A. Lindberg

Mobile cranes on tires are perhaps the most important accessory in truck-haulage pits. They usually are of 20-ton capacity at short radius and with outriggers but have considerable overload capacity. Standard booms are 30 ft but have 10-ft extensions with which they are usually operated. Cranes have two engines, both originally gasoline, but 150-hp Diesel engines have been found more reliable for the propulsion motor, the 100-hp gasoline motors being retained for hoisting. Pro- visions are made for dropping the ballast counter- weight to reduce axle weights to legal limits for highway travel. The weights are carried on a regular truck or are transported on an extra trailer axle behind the crane. Tractors-Probably equalling the cranes in usefulness are the track-laying tractors which are used to prepare roads and other surfaces, to clean up at the shovel, and for dozing on stripping dumps. A new type of tractor mounted on rubber tires has been tried out on the Mesabi Range for the past year and a half. The advantage of this design is its mobility which makes it capable of taking care of the spill at the shovel and then running to the dump to clean up. Alternating between these two jobs, it relieves heavy tractors that can be used to better advantage on heavier work that does not require so much traveling. This tractor can travel at speeds of 12 to 13 mph and is designed to facilitate repair of the expendable parts. Weaknesses have developed in the internal construction which have seriously marred the performance record of this unit, but when used within its capacity it is quite successful.

Jan 1, 1949

By G. Thomas, O. Johari

MEIERAN and Richman' have proposed a method for the determination of electron-diffraction patterns from twinned bcc crystals. It is the purpose of this note to present a general method capable of predicting the positions of all reflections from both matrix and twin regions for all possible orientations of cubic crystals. The method has been verified for twinning in explosively deformed copper, and is found to be a very useful tool when used in conjunction with stereographic projection, and dark-field electron microscopy. Let an isometric crystal be twinned in any (hkl) plane. The twinning can be considered either as a reflection in the twin plane or as a 180-deg rotation about the twin axis. In reciprocal space, the 180-deg rotation about the twin axis would place a given point p, q, Y to a new position P, Q,R, such that both will be equally inclined to the twin axis. This is represented in Fig. 1. If the coordinates of three such pairs of points are determined, the matrix of the transformation can be obtained.' It is also seen that such pairs would satisfy another condition, i.e., the vector [p,q,r] plus the vector [P,Q,R] will yield a multiple of hkl, i.e., the indices of the twin plane, because in isometric systems the axis [hkl] is perpendicular to the plane (hkl). This can be simplified by taking the points along the three axes. If a point h2 + k2 + 12, 0, 0 is taken along the x axis, it is seen that its new indices should be so as to yield a sum 2h2, 2hk, 2hl,i.e., 2h(h,k,1). (Also the points h2 - k2 - 12, 2hk, 2h1, and h2 + k2 + 12, 0, 0 are equidistant from the origin and both points make equal angles with the twin axis, i.e., cos-' h/dh2 + k2 + l2.) Similar operations for the points yield respectively, after the 180-deg rotation about the twin axis. Following the method due to Buerger,' the matrix of the transformation is obtained as follows: Using this matrix the indices of any other point in reciprocal space can be determined. This matrix is much simplified for (111) twinning commonly encountered in fcc metals, since are each equal to —1; hence

Jan 1, 1964

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods' for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

By Sherwin F. Kelly

THOUGH the Geophysics Commit- tee limited itself to two sessions this year, both of them marked by a high percentage of absentee authors, even this situation failed to dampen the and or of the ebullient geophysicists, who bandied no small amount of good- humoredlv barbed discussion. Hans Lundherg offered some constructive criticism of last year's report by the Geophysics Education Commit- tee, making a plea for more training in field techniques and less insistence on rigorous theoretical training. Carl Heiland pointed out the necessity of making geophysics and geology courses more attractive in order to draw more students into these fields. Exception was taken to this line of reasoning by Father Macelwane and Sherwin F. Kelly who emphasized the necessity for sound basic training if competent geophysicists were to be turned out. This discussion developed apropos of the report of the Geophysics Education Committee, which had been postponed from the Education Division meetings, but was not read as it was available in mimeographed form. Except for this diversion the morning program fol-

Jan 1, 1944

E. E. Olcott, New York City: Prof. Kemp's valuable description of the Lancaster Gap mine is in line with many other able contributions on the origin of mineral deposits that the Institute has lately brought forward. The splendid contribution that Prof.

Jan 1, 1895

By AIME AIME

NAPOLEON'S dictum that an Army travels on its stomach has not changed in this present war, but the things an Army's stomach calls for would be more than strange to Napoleon. Today one of the main articles of diet for the mechanized army is oil and gasoline, and the chief and most efficient source of 'apply overland is the pipe line. It was a flexible 4-in. pipe line that supplied the voracious appetite of tanks, trucks, jeeps, and planes across the North African desert. and it is the 1800-mile pipe line from Calcutta to Kunming, Yunnan Province in China, the longest in the world, that supplied oil and 100-octane gas for the trucks, tanks, Jeeps, and planes fighting on the Assam-Burma-China front in recent months. Completion of this approximately 1800-mile pipe line to China over rivers that had never been bridged, over hill that towered 9000 ft., and over swamps

Jan 1, 1945

By D. N. Hedges

This paper discusses the actual recovery and installation of a longwall in a bituminous coal mine in western Pennsylvania. The coal bed mined is in the Lower Freeport seam, which averaged 1.07 m (42 in.) in height locally. Drainage from the mine is about 13.25 ML/day (3.5 million gal per day) of water. This water deteriorates the mine's predominately fire clay bottom making it extremely difficult to move equipment. Support removal is accomplilshed by pulling the 5.44 t (6 st) shields out under their own hydraulic power and transporting them by track 8.05 km (5 miles) to the next longwall panel. This paper also discusses the changes that will be made to aid in the succeeding longwall recoveries and installations.

Jan 1, 1985

By J. F. Poland

B. C. Burgess-—Prior to hearing this paper presented at the San Francisco meeting, I travelled by car from Yuma, Ariz., across south-central California and up through the San Joaquin Valley. After hearing the paper I returned by the coast route to San Diego then along the Mexican border to Yuma. The striking feature of these trips, related to this paper, was the dry river and creek beds at a time of year not the dry season. Contrasted with this was the wasteful use of water in irrigation canals and laterals. Poland says "at least 90 pct of the ground water pumped is used for irrigation." That being the case, it would appear that first consideration should be given to conservation of this use. Probably a small part of this is actually reaching the plants. Some measure of this loss between pump and crops would be revealing. Methods that might be employed to reduce this loss are pipe lines and spraying of some crops such as the banana planters are using in Central America. Another idea which might be investigated is to line canals and ditches with some water-repelling mineral like pyro-phyllite. Perhaps a comparatively thin sprayed-on

Jan 1, 1951

By J. F. Poland

B. C. Burgess-—Prior to hearing this paper presented at the San Francisco meeting, I travelled by car from Yuma, Ariz., across south-central California and up through the San Joaquin Valley. After hearing the paper I returned by the coast route to San Diego then along the Mexican border to Yuma. The striking feature of these trips, related to this paper, was the dry river and creek beds at a time of year not the dry season. Contrasted with this was the wasteful use of water in irrigation canals and laterals. Poland says "at least 90 pct of the ground water pumped is used for irrigation." That being the case, it would appear that first consideration should be given to conservation of this use. Probably a small part of this is actually reaching the plants. Some measure of this loss between pump and crops would be revealing. Methods that might be employed to reduce this loss are pipe lines and spraying of some crops such as the banana planters are using in Central America. Another idea which might be investigated is to line canals and ditches with some water-repelling mineral like pyro-phyllite. Perhaps a comparatively thin sprayed-on

Jan 1, 1951

By F. P. Haver, M. M. Wong

When a mixture of chalcopyrite concentrate and lime is heated in air, the following reaction takes place: 2CuFeS2 + 4Ca (OH)2 + 8 ½ 02 ; 2Cu0 + Fe203 + 4CaS04 + 4H20. Ca (OH)2 is the only common reagent that will adequately control SO2 evolution in roasting. Other additives tried, including CaO, CaCO3, Na2CO3, NaOH, MgO, Mg (OH)2, and MgCO3, were not effective. All reacted with sulfur, but not to the extent that will be required to meet the new control regulations for sulfur oxide emissions. For example: when the concentrate was heated with the theoretical amount of limestone (CaCO3), about 55% of the sulfur was retained in the calcine; whereas use of the stoichiometric amount of Ca (OH), converted approximately 99% of the sulfur to CaSO1. In most of the experiments, Ca(OH)2 was formed by adding CaO to concentrates containing enough water to simulate filter cake from flotation circuit. This eliminated the need for drying the concentrate and utilized the heat of hydration of CaO.

Jan 6, 1972

By AIME AIME

ON March 14, the University of Tulsa was accepted as a member of the North Central Association of Colleges, which ranks Tulsa among the leading universities of the country. A. G. OIiphant recently donated to the new school of petroleum engineering a splendid collection of books on geology, valued at $25,000. Waite Phillips, an oil producer and chairman of directors of The Independent Oil & Gas Co., donated $150,000 for a petroleum engineering building

Jan 1, 1929

By AIME AIME

T HE Mid-Continent Section of the Petroleum Division met on Mar. 11 in the engineer's room of the Tulsa Building, Tulsa, Okla., for the purpose of reviewing the papers presented at the annual meeting in New York. L. G. E. Pignell, chairman and delegate to New York for the Mid-Continent Section, read a brief report giving the outstanding features of the various papers that were presented. He expressed regret that more members of the Division could not be present in New York to hear the interesting papers and discussions. It was his opinion that the various remedies presented for overproduction seemed rather theoretical and impractical and he recommended that the engineers come to the aid of some of the economists in giving more practical consideration to the overproduction problem.

Jan 1, 1929

By Franklin G. Pardee

WARTIME depletion of the reserves of iron ore in the Lake Superior region of the grade and character now being shipped down the Lakes was serious. The time has come to take stock of the resources that remain in order to plan our future program of supply for our blast furnaces and protect, as far as possible. the tremendous investment made in the Lake Superior iron mining industry. Hugh M. Roberts and William H. Crago have estimated the reserves of the Lake Superior region in the United States at two billion long tons. These reserve figures are of direct-shipping ore and those concentrates produced by methods now in commercial use or those methods that may be expected in the near future. In their estimate they have assigned 392 million long tons to the Michigan ranges (all reserves in long tons) : 112 million tons for the Gogebic. 140 million tons for the Menominee, and 140 million tons for the Marquette.

Jan 1, 1948

By P. Beardmore, B. W. Howlett, B. D. Lichter, M. B. Bever

The heats of formation at 273°K of the compounds Mg2Ge, Mg2sn, and Mg2b, the heats of fusion and melting points of Mg2Sn and Mg2Pb, and the heats of solution of magnesium, germanium, and lead in liquid tin have been measured. The excess free energies of the liquid alloys and the free energies of formation of magnesium-Group IVB compounds at their melting points and their standard free energies of formation at 298°K have been calculated. The stability and bonding of the compounds are discussed with reference to these properties. Some thermodynatnic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. THE compounds of magnesium with the Group TVB elements, silicon, germanium, tin, and lead, have often been considered to constitute a nearly ideal homologous series. In particular, their thermodynamic stability has been assumed to decrease with increasing atomic number of the Group IVB element.' The binary-phase diagrams of the magnesium-Group IVB elements given by Hansen and Anderko2 have the same form. Each system has a single con-gruently melting compound of limited homogeneity range. The structures of these compounds, which have the formula Mg2X, are anti-isomorphous with the calcium fluoride structure. A recent investigation has found evidence of a second compound in the system Mg-Pb.3 The solid compounds Mg2Si, Mg2Ge, and Mg,Sn are semiconductors, while the conductivity of Mg2Pb approaches that of a metallic conductor. This difference suggests that other properties may also show a discontinuity. The investigation reported here is concerned with the thermodynamic properties of magnesium-IVB compounds and particularly their variations with the period of the Group IVB element. The heats of formation at 273°K of the compounds MgzGe, Mg2Sn, and Mg2Pb and the heats of fusion and melting points of Mg2Sn and Mg2Pb have been measured. The results, combined with published data, are interpreted in relation to the stability and the bonding characteristics of the compounds. Some thermodynamic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. In the course of the investigation the heats of solution of magnesium, germanium, and lead in liquid tin have been determined. 1) EXPERIMENTAL PROCEDURES 1.1) Samples. Samples of the compounds Mg2Ge, Mg2Sn, and Mg2Pb, supplied by Professor P. Aigrain, Compagnie Générale de Télégraphie Sans Fils, were used in measuring heats of formation, heats of fusion, and melting points. Samples of Mg2Sn and Mg2Pb, supplied by Dr. V. B. Kurfman, Dow Metal Products Co., samples of Mg2Sn, prepared at the Air Force Cambridge Research Laboratories, and samples of MgzPb, prepared in this laboratory, were used for additional measurements of the heats of fusion and the melting points. The samples were stored in evacuated Pyrex capsules or under nonreacting liquids. 1.2) Heats of Formation. The heats of formation at 273°Kof the compounds Mg2Ge, Mg2Sn, and Mg,Pb were measured by tin-solution calorimetry. In this method, samples of the compound and of a mixture of the constituent elements are added alternately from 0°C to a tin-rich bath. The difference between the heat effects, corrected for the change in composition of the bath, is the heat of formation of the compound. Details of the method have been given elsewhere. 4 The bath was maintained at 350°C for the dissolution of the compounds MgzSn and Mg2Pb. Since at this temperature the dissolution of Mg2Ge was too slow, a bath temperature of 400" or 450°C was used with this compound. At least three calorimetric runs, each of approximately six additions, were made with each compound. 1.3) Heats of Solution. The determination of the heats of solution of magnesium, germanium, and lead in tin was included in this investigation because they were not well-established at the time this work was started. To obtain the heat of solution, the difference

Jan 1, 1967