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THOMAS L. WATSON,* Charlottesville, Va. (written discussion ? ).¬Sphalerite, as is well known, occurs not only as a common constituent of many types of ore deposits formed under widely varying geologic conditions, but its sulphide mineral associates comprise a goodly number of species. In the investigation by Mr. Teas, data were obtained from a mineralographic study of about 200 ore specimens from 43 different localities grouped according to their genesis as follows: (1) Contact-metamorphic deposits, (2) deep-vein zone deposits, (3) intermediate-vein zone deposits, (4) shallow-vein zone deposits, (5) meteoric water deposits. .The object of the study was to determine the relations of sphalerite to the associated sulphide minerals and their possible genetic significance. As a result of the investigation, Mr. Teas has deduced several important conclusions. Probably the one of largest interest and value was that sphalerite formed from magmatic waters, including contact-metamorphic, deposits, could be distinguished, for the cases investigated at least, from sphalerite formed from meteoric waters, by development in the former of minute triangular or rectangular dots or stringers of chalcopyrite. Although chalcopyrite inclusions in sphalerite had been noted by previous observers, the probable significance of their apparent general occurrence in sphalerite of certain types of ore deposits and their absence from others was unknown. The large number of ore specimens studied from more than 40 different localities in the United States and foreign countries, representing the principal genetic types of sphalerite-bearing deposits, gives considerable weight to the conclusions reached by the author. Should the conclusion drawn by Mr. Teas become generally applicable, a laboratory criterion of much value will have been established for distinguishing between sphalerite formed from juvenile and that from meteoric waters. The principle seems applicable not only to sulphide deposits in which sphalerite is the principal constituent, but to those in which it occurs as a very subordinate one, as shown by the study of ore specimens from one of the principal pyrite mines in Virginia. It may be possible also that the principle will have important application in differentiating primary from secondary sphalerite occurring in the same deposit formed from magmatic waters, although there have-been comparatively few well-

Jan 4, 1918

By N. W. Ratliff, P. J. Closmann

Production of oil by expansion from a cylindrical reservoir composed of two concentric regions of different properties has been determined as a function of time for a reservoir producing at constant terminal pressure. The parameters involved are permeability, porosity, compressibility and oil viscosity. Results agree with those of a generally accepted method for uniform reservoirs when all parameters are taken as uniform. Cumulative production at any given time is reduced below that of the uniform reservoir when a region of considerably lower permeability adjoins the well; cumulative production increases when a high-permeability region adjoins the well. Curves are presented illustrating quantitative effects of these variations. INTRODUCTION Most petroleum reservoirs can be exploited by release of pressure and consequent expansion of underground fluid. During part of the production history of certain reservoirs by this mechanism, fluid compressibility can be considered small and constant. Cumulative fluid produced by this means as a function of time was calculated for a uniform reservoir by van Everdingen and Hurst.l For certain cases where a production well has been damaged or where an acid treatment has been used, a zone of properties different from those of the reservoir may be created around the production well. In such a case, expansion of the reservoir fluid takes place in a system composed of two concentric cylindrica1 regions of different reservoir properties. Such composite systems were studied in connection with heat flow by Jaeger2 who presented a solution for temperature distribution in a radial system with an infinitely large outer radius. Similar heat flow problems have been studied by other authors Oil production from composite reservoirs was studied for constant production rate by Hurst,4 Loucks and Guerrero,5 and Carter.6 THEORY This work considers constant terminal pressure. Cumulative flow is calculated for a composite bounded system in which no flow takes place across the outer boundary (Fig. 1). Since the flow is considered to be purely radial, the problem involves only one space dimension and time. It is convenient to define the following dimen-sionless pressure drops (Fig. 1).

By J. Campbell

Long freezing range casting alloys are particularly susceptible to a type of porosity which is observed to form in layers parallel to the supposed position of the isotherms in the solidifying casting. Under favorable conditions (which appear to be typified by low-temperature gradients in the casting giving rise to a wide and more or less uniform pasty zone, and which arise from several factors, particularly: a) wide freezing range alloy, b) high thermal conductivity of metal, c) low thermal conductivity of mold, and d) high mold temperature3) layer porosity has been observed in many different casting alloys: copper,' aluminum, magnesium,' steels, and high-temperature alloys.3 Baker4,5 and later cibula6 argue that layer porosity occurs because of thermal contraction, in a manner analogous to hot tearing. In outline, the theory consists of the establishment of a coherent dendrite network by the impinging of dendrite tips. Subsequent shrinkage imposes tensile stresses on the network which tears perpendicularly to the stress, i.e., parallel to the isotherms. If these tears are not filled by the inflow of residual liquid then layers of porosity result. Baker7 attempted to test whether the porosity was the result of thermal contraction by casting test pieces in a mold designed to accentuate hot tearing. However, no significant increase in porosity was observed. This negative result of Baker's critical experiment appears to be substantiated by numerous observations, particularly the experiments by Lagowski and Meier8 on Mg-Zn alloys covering the range of zinc contents up to 30 pct Zn. These clearly reveal that the maxima for the incidence of hot tearing and layer porosity are well-separated, occurring at 1 and 6 pct Zn, respectively. Furthermore, the thermal contraction maximum occurred at 1 pct Zn, indicating that hot tearing is associated with contraction in the solid state, and not with porosity. These observations are further substantiated by the elementary consideration that the thermal contraction of the casting is likely to produce (if anything, since the temperature difference across casting of high thermal conductivity, such as aluminum and copper, is likely to be negligible) a compressive stress on the

Jan 1, 1969

THE increased demand for titanium alloys with improved high-temperature creep strengths has stimulated interest in silicon as an alloying addition to titanium. Silicon is a potent solid-solution strength-ener and, if added in sufficient concentration and properly heat-treated, can also dispersion-strengthen titanium by eutectoid decomposition.' However, better understanding of the nature and distribution of the resulting silicide dispersion in more highly alloyed titanium matrices is necessary for the development of useful titanium alloys which utilize the latter strengthening mechanism. This note describes the chemical and crystallographic characteristics of the silicide phase as it occurs in a typical high-temperature near-a titanium alloy matrix. Several Ti-6A1-3Sn-3Zr a11oys containing various amounts of silicon ranging from 0.1 to 1.0 pct were melted as 10- to 20-lb ingots and processed into 1/2-in.-diam bar stock. The microstructures of specimens annealed at various temperatures were conveniently summarized by the (Ti-6Al-3Sn-3Zr)-Si pseudobinary phase diagram illustrated in Fig. 1. Comparison with the Ti-Si equilibrium diagram indicates the substitutional solutes (Al-Sn-Zr) increase the eutectoid temperature and decrease the a terminal solubility. Annealing at temperatures sufficiently high to dissolve the silicon in a ß solid solution and cooling rapidly enough to preclude coarsening generally produced a uniform dispersion of fine silicide particles, whereas annealing at temperatures near but below the ß transus produced relatively coarse silicide particles. Annealing in the limited a, plus 3 region produced a duplex coarse and fine silicide array. Several a-annealed specimens were examined by X-ray diffraction to determine the crystallographic identity of the precipitate phase. Copper Ka X-ray diffraction patterns of bulk specimens which contained 0.5 and 0.8 pct Si were virtually identical to that of the silicon-free Ti-6Al-3Sn-3Zr base alloy except for a slight shift in some of the high-angle diffraction lines. Apparently the silicide volume fraction was too low to be detected in bulk specimens. X-

Jan 1, 1969

By H. C. Hardison

The Yates pool, Pccos County, Texas, has greater potential capacities than any other field in the United States. This field is notable for the large return it yields on capital invested, for low production costs and for the orderly and conservative manner in which it was developed and continues to be operated. The proven area is 20,000 acres and there are 392 producing wells, or approximately 1 well to 50 acres. The theoretical daily potential is 5,250,000 bbl. as determined by l-hr. open-flow gages. Individual well gages vary from a few barrels to 8500 bbl. per hour, and well depths range from 1000 to 1800 ft. The greater part of the production is from a very porous limestone, and by agreement no productive well has penetrated the lime more than 225 ft. The forces driving the oil from the formation to the surface are hydrostatic head, expanding gas or a combination of the two. The degree of effectiveness of either depends upon the structural position of, and porosity encountered in, the individual wells. Approximately 95 per cent. of the wells in the field flow naturally. The pipe line outlet of the field at the present time is 100,000 bbl. per day, which is less than 2 per cent. of the daily potential. Difficulties and Principles of Probation It became evident during the first year of the development of this field that operators would have to devise a scheme to allocate pipe line runs equitably among their different properties. When the idea of proration was first inaugerated, the matter of spacing wells was given consideration. This was given up through fear of legal difficulties. Storage was also a question that was given considerable thought, and a plan was finally developed which went into effect Oct. 1, 1927. It was decided that the oil runs should be prorated according to the total potential capacity of all the wells which the several operators had in the field. The potential capacity of the wells was measured by a l-hr. open-flow gage. All runs to storage by an operator were deducted from his daily allowance.

Jan 1, 1931

By R. G. Davies

Isothermal annealing of quenched Fe3Al reveals that the superlattice forms by the nucleation and growth of ordered domains. The activation energy for isothermal ordering and initial domain growth is -29 keal per mole, which is thought to he the activation energy for vacancy migration. Domain growth, in the absence of excess vacancies, has an activation energy of -100 keal per mole. A maximum in the hardness is observed when the structure consists Of ordered domains, -35-4 in size, growing into a short-range ordered matrix and, also as a function of degree of order, S, with an infinite domain size at S = 0.4 to 0.5. It is proposed that both maxima are due to a transition from deformation by unit dislocations to deformation by superdislocntions. FE-AL alloys containing more than -23 at. pet Al, when quenched from above the critical temperature for the Fe3A1 type of order, always contain the maximum possible amount of FeAl (B2) type of order' (see Fig. 1). Thus when the Fe3A1 superlattice forms, in a 25 at, pet A1 alloy, it does so from an imperfect FeAl structure. The formation of the Fe3Al superlattice has been the subject of several recent X-ray,1, 2 electrical-resistivity,3"6 and dilatometric3 investigations. McQueen and Kuczynski3 concluded that the isotherma1 ordering of Fe3Al, after quenching from 800°C (T,, the critical temperature for order, is 55O°C), takes place by the nucleation and growth of ordered domains. However, Feder and Cahn4 found that the isothermal ordering was complex but more like a homogeneous nucleation process than a nucleation and growth process. Lawley and Cahn2 reported that the degree of order is a continuous function of temperature which is a characteristic of a homogeneous nucleation process. Thus, the evidence is conflicting as to the nature of the Fe3Al ordering reaction. Lipson7 was the first to suggest that ordered domains should exist in the Fe3A1 structure since, as

Jan 1, 1964

By John P. Hager, Adolfo R. Zambrano

The thermodynamics properties of the liquid Pb-Ag-Au system have been determined from galvanic cell measurments five pseudobinary systems of fixed XAg/XAu ratio. The galvanic cell employed a molten PbO-SiO2 electrolyte and was operated between 775" and 1030°C. The thermodynamics properties of lead were obtained directly from the experimental data, whereas the excess integral molar properties and the activities of silver and gold were obtained by means of the Gibbs-Duhem equation. The calculated proper -ties of the Ag-Au system agree well with the published properties. The liquidus surface of the Pb-Ag-Au system has been determined at 1200°K. In Parts I' and 11' the galvanic cell Mo,Pb(l)|(PbO-SiO2)(l) SiO2(s) |Pb(alloy)(l), Mo [I] was used to determine the thermodynamics properties of the Pb-Ag and Pb-Au systems, respectively. The use of cell I, in which a molten oxide electrolyte is employed rather than the classical fused-salt electrolyte, was shown to result in more accurate ther-modynamic measurements in that the displacement reaction at the alloy-electrolyte interface (l/Zb)B(alloy) + (I/za)A+Za = (1/Za)A(alloy) + (1/Zb)B+zb [1] was minimized. For the Pb-Ag system, where B = Ag(l), the error in the activity of lead (aPd) re-sulting from Reaction [I] was calculated to be less than 1 pct.l For the Pb-Au system the error in aPb was calculated to be less than 0.5 pct.2 Also, electro-transport measurements on the PbO-SiO2 electro-lyte1,2 established that the conduction was entirely ionic and that lead was present only in the divalent state. In the present study the experimental technique is extended to an investigation of the thermodynamic properties of the liquid Pb-Ag-Au system. Five pseudobinary systems of fixed X Ag/XAu ratio were selected. The experimental results were then combined with the previous measurements on the component binary systems Pb-Ag1 and Pb-AU2 to calculate, by means of the Gibbs-Duhem equation, the molar and partial molar mixing properties for the liquid ternary solutions.

Jan 1, 1970

By John T. Crawford

Much has been written of late regarding the flotation of coal as a means of reclaiming the valuable portion of the fines encountered in nearly all methods of coal preparation. Whether the process be wet or dry, whether the dust be sent through the entire process or removed prior to the cleaning by some such method as screening or aspiration, one of the final products consists of a considerable proportion of — 48-mesh material. The percentage of this —48-mesh material depends upon the mining method, transportation, storage, and method of preparation. The tonnage of this dust material ranges from 1 to 10 per cent of the total output of the cleaning plants. Four methods of disposal are available for this coal: 1. Disposal with the refuse from the plant. 2. Addition, after being reclaimed from the wash water, or dust collectors, without cleaning to the larger sizes. 3. Separate disposal as a pulverized fuel. 4. Cleaning so that addition to the larger sizes benefits the product as a whole. It is also true that flotation in one form or another is the only known way to effectively clean this material. While some processes do a reasonable cleaning job down to and including +l00 mesh, by far the greater majority stop at or short of the + 48-mesh size. Much of the literature on coal flotation passes by the fred pulp density and size by merely stating that the feed varies from 20 to 30 per cent solids and that the size range is from — 1/4 in. or — 1/8 in. to 0. Small wonder then that some operators with entirely different conditions, and not knowing the machine capacity, throw up their hands in despair when flotation is mentioned. Too much parallel is drawn between flotation methods as applied to ores and as applied to coal, to the detriment of the latter. In the flotation of metalliferous ores the feed pulp density ranges from 20 to 30 per cent solids, depending upon the amount of mineral to be floated and upon the size analysis. Thus where 2 to 5 per cent of the

Jan 1, 1936

By Robert H. Richards

THE Institute of Mining Engineers has shown so much interest in the educational problem of profitably combining theory and practice, that it seems especially appropriate to lay before its members the methods and aims of the mining laboratory of which I have charge, and in which one form of combination of hand with head work is now being tried. If anything may be contributed toward the solution of this problem by the discussion which follows, my purpose mill be attained. Whether it was wise or not to establish a mining school so far from the principal mining centres, does not now enter into the question. Given, a mining school already begun, how shall it be made most efficient in developing engineers who are trained to think for themselves as well as versed in the works of others ? This is the question with which we have had to deal. In considering the bearing of this laboratory work upon the students' preparation, it will be convenient to take it up under five different heads: 1. The methods and aims of the laboratory. 2. The advantage to students of having a part, at least, of their practical work in the curriculum of their school. 3. The advantage to be derived by mine; and works. 4. Degree of accuracy which may be attained in working ores on a small scale. 5. Reslts of work in the laboratory. 1. The Methods and Aims of the Laboratory.—During the May meeting of 1873, held in Boston, I had the privilege of reading before you a paper stating the plan; and aims of this laboratory. Since that time me have been constantly following out those plans, and are more than ever convineed that me are working in the right direction. We do not feel that the time we have spent has been in any sense thrown away. Perhaps the aims of the laboratory can be most clearly shown by illustration. Many young engineers have school thinking that they know everything. They go to the works, and expect to teach the superintendent something and the men a good deal, regardless of the fact that it is this spirit that has prejudiced workmen against schoolmen. They are often more trouble than they

Jan 1, 1879

By John T. Crawford

Much has been written of late regarding the flotation of coal as a means of reclaiming the valuable portion of the fines encountered in nearly all methods of coal preparation. Whether the process be wet or dry, whether the dust be sent through the entire process or removed prior to the cleaning by some such method as screening or aspiration, one of the final products consists of a considerable proportion of — 48-mesh material. The percentage of this —48-mesh material depends upon the mining method, transportation, storage, and method of preparation. The tonnage of this dust material ranges from 1 to 10 per cent of the total output of the cleaning plants. Four methods of disposal are available for this coal: 1. Disposal with the refuse from the plant. 2. Addition, after being reclaimed from the wash water, or dust collectors, without cleaning to the larger sizes. 3. Separate disposal as a pulverized fuel. 4. Cleaning so that addition to the larger sizes benefits the product as a whole. It is also true that flotation in one form or another is the only known way to effectively clean this material. While some processes do a reasonable cleaning job down to and including +l00 mesh, by far the greater majority stop at or short of the + 48-mesh size. Much of the literature on coal flotation passes by the fred pulp density and size by merely stating that the feed varies from 20 to 30 per cent solids and that the size range is from — 1/4 in. or — 1/8 in. to 0. Small wonder then that some operators with entirely different conditions, and not knowing the machine capacity, throw up their hands in despair when flotation is mentioned. Too much parallel is drawn between flotation methods as applied to ores and as applied to coal, to the detriment of the latter. In the flotation of metalliferous ores the feed pulp density ranges from 20 to 30 per cent solids, depending upon the amount of mineral to be floated and upon the size analysis. Thus where 2 to 5 per cent of the

Jan 1, 1936

By J. A. Solomon, H. E. Shafer

As a result of the great demand for metallic aluminum and the scarcity of domestic bauxite, numerous processes have been proposed and developed to extract the oxide of this metal (Al2o3) from clays, shales, and other low-grade raw materials.1-4 An exploratory study was made to extract alumina with sulfuric acid from relatively impure coal-associated draw-slate and to establish an optimum calcination temperature for maximum recovery. Draw-slate is the term used to describe the hard, slaty material directly overlying many coal seams and may range from a few inches to a few feet in thickness. Alumina content of these draw-slates may range from as low as 15% to over 35%. Although the following results are limited in scope, some of the data should prove beneficial for further work. Coal-associated clay, shale, and gob heretofore have been considered nuisance products; any successful alumina extraction process would greatly enhance the worth of these almost limitless resources. This research demonstrated that an optimum calcination temperature for alumina extraction could be established for a coal-associated draw-slate and that this temperature was lower than those suggested in previous work with unspecified clay types. It should be noted that slightly higher acid concentrations and somewhat finer particle sizes were used in this series of tests as compared to previous work. EXPERIMENTAL WORK Essentially, alumina extraction proceeded in four steps: 1) grinding, 2) calcining, 3) acid leaching, and 4) precipitating of aluminum sulfate. An initial series of reference tests to determine the optimum temperature of solubility for alumina was run using relatively pure kaolin. Kaolin forming clays are hydrous aluminum silicates of the approximate composition 2H2O A12O3 2SiO and kaolinite is the mineral that predominates in most kaolins. 5 The kaolin was ground to -30 mesh and subsequently calcined at temperatures ranging from 100°C to 700°C. Each sample was calcined for 1 hr in a muffle furnace and in turn subjected to sulfuric-acid leaching (H2SO4, 9 molar) for a 2-hr period. The filtrates were analyzed for the amount of dissolved alumina recovered.637 Also, each sample of leached or barren residue was

Jan 1, 1968

By H. W. Kerr, B. Soutiere

THE possibility of using unidirectionally solidified eutectic alloys as high-strength composite materials has been investigated by several workers. Unidirectionally solidified lamellar and fibrous eutectics have been shown to have good short-time structural stability at temperatures close to the eutectic melting temperature.'-4 Several investigations of both short-time high temperature tensile properties and creep properties of eutectic alloys have been carried out,3-" with promising results. Little work has been reported, however, on the thermal stability of eutectic alloys which have been unidirectionally solidified and subsequently deformed in compression. Since processes such as rolling and grinding introduce compressive stresses, and since the properties depend on the spacing and perfection of the composite structure10,11 this aspect is of definite importance if unidirectionally solidified eutectic alloys are to be considered for commercial use. A Cd-Zn alloy made from 99.999 pct starting materials was cast into a graphite boat and zone levelled12 to obtain a completely lamellar structure at one end of the bar. Sections from this region of the bar were removed, recast into 6.5 mm I.D. Pyrex tubing, and solidified unidirectionally upwards at a rate of 2.8 cm per hr. Specimens were cut from the solidified rods, heated in air at 200°C (0.88 of the eutectic melting temperature) for various lengths of time, and examined metal-lographically. Compression specimens were also cut from the solidified rod carefully machined to a length of & in., and deformed with the compressive axis parallel to the original growth axis to produce a total longitudinal strain of 12 pct. Some of these specimens were examined metallographically; others were heated in air at 200°C for various lengths of time and then examined. Metallographic examination of the deformed specimens showed the two types of deformation previously described; slip lines13 (smoothly bent lamellae) and kinks13,14 (sharply bent lamellae). Very close to the specimen ends there were a large number of deformation bands, but at a distance of about -re- in. the deformation was very localized, as shown in Fig. 1.

Jan 1, 1970

GEORGE S. RICE (written discussion *).-An interesting and important question arose during the coal famine of last winter as to whether the development of new mines should be discouraged on account of the need of labor for the necessary construction and development work at a time of scarcity of labor, more especially as there was an apparent overcapacity of existing mines. The question was referred to the author for his comments, which led to the study of the statistics. The essential results of this study are indicated on the accompanying chart, which illustrates, among other things, the increase in production or consumption, and the estimated maximum production capacity of the bituminous and sub-bituminous mines of the United States. The curves shown are based on data published in the "Mineral Resources" of the United States Geological Survey, and cover the period from 1900 to 1916 inclusive. The following curves have been drawn from the data secured: 1. Average number of days that the mines worked. 2. Yearly total production of bituminous and sub-bituminous mines. 2a. Yearly production of machine-mined coal. 3. Average annual production, equivalent to consumption, for a period of 17 years. 4. Number of coal mine employees each year. 5. Estimated capacity of mines, on basis of 300 working clays in the year. 6. Estimated drop in capacity if no new mines are opened. Considering these curves and the data from which they were constructed: It will be noted that the average number of days the miners worked varied from 193 in 1908 to 234 in 1900, the average being 217. The causes for so many idle days out of the possible total number of working days in the year are well known, namely: (a) Lack of business; (b) lack of cars. Taking the country as a whole, (a) is the important factor, which might otherwise be expressed as being an excess of productive capacity. The yearly production of the mines, which is practically synonymous with consumption, has shown a steady increase, with a few set-backs. An average line has been struck which indicates that the average annual increase of production has been 18 million short tons (16,330,000 metric tons).

Jan 5, 1918

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

By Elliott J. Roberts

In spite of the fact that the percentage of true colloids in an ore grind is very small,' these pulps exhibit many of the properties of true colloidal suspensions. A quartz particle, appreciably finer than 10 microns in diameter, has a settling rate so low that at a dilution of 5:l or over, the capacity of a settling tank to settle such particles would be uneconomical if the individual particle rate prevailed. However, by grouping the finer particles into aggregates or flocs, the settling rate can be increased to an economical value. The colloidal chemistry of pulp thickening is thus chiefly concerned with particles having diameters of between 1 and 10 microns, although particles as coarse as 40 microns in diameter are more or less involved. These particles must be associated in such a manner that they settle at an economical rate and give a clear, supernatant liquid or overflow. The treatment of the subject may be divided into three phases, cach phase having a more or less different colloidal aspect. The first phase is the problem of getting the pulp or suspension into the proper condition of flocculence; the second is the behavior of the flocculent pulp in its initial and intermediate stages of settling; the third is the behavior of the flocs in the find period of settling or thickening stage. Let us look first into the methods and mechanism of obtaining the flocs and then consider their behavior and properties. Flocculation Colloids are merely ordinary substances reduced to a very small particle size, the upper limit being placed by definition at 1 micron (0.001 mm.) diameter by the soil chemists and at from 0.2 to 0.1 micron by various other colloid chemists. The lower limit is reached only when the particles approach molecular dimensions. The term L'colloid" should not necessarily imply lack of crystallinity. Particles as small as 0.01 to 0.02 micron give perfect X-ray patterns, while with 0.005 micron particles the bands on the powder photograph are merely broaderled and diffused.2

Jan 1, 1935

By D. G. Westlake, E. S. Fisher

The habit planes for zirconium hydride precipitation in crystals of a zirconium have been determined at various hydrogen concentrations. The (10 • 0)planes are the predominant habit planes; some (10 • 5) and (10 -1) planes were observed after charging conditions which pevmitted formation of a surface layer of hydride. No platelets zrlere observed parallel to any of the twinning planes. Mechanisms for em-brittlement due to hydride precipitation are discussed. LANGERON and Lehr1 found, in 1956, that zirconium hydride precipitates in zirconium in platelets lying parallel to (10.0) slip planes. In 1960, Kunz and Bibbz reported observing the platelets in three different families of twinning planes, (10.2) {11.1), and {11.2), but never in the slip planes. The present study was undertaken to ascertain the cause of these seemingly contradictory results. EXPERIMENTAL Two specimens of iodide zirconium were used in the experiments. Specimen I was a single crystal, while specimen II contained three grains. Grain growth was accomplished by the technique of Lange-ron and Lehr. Three faces were ground on specimen I; the first was 2 deg from the (00.1) basal plane, a second was 2 deg from the (10.0) prism plane, and a third was 4 deg from the (12.0) plane. One face was ground on specimen II such that the poles of the surfaces of crystals A, B, and C were as shown in Fig. 1. After the faces were ground on 600 grit silicon carbide paper, they were chemically polished by dipping in a solution of 8 parts hydrofluoric acid, 50 parts nitric acid, and 50 parts water. This removed all cold worked metal from the surface. The samples were charged to various levels of hydrogen content by heating in hydrogen gas which had been purified by reaction with uranium powder. The various charging conditions are shown in Table I. Specimen I was heated to the reaction temperature at the indicated hydrogen pressure and allowed to react until essentially all the hydrogen was used up. Then the temperature was raised for homogenization. Specimen II was charged by making periodic addi-

Jan 1, 1962

By William A. Edmiston, R. E. Grace

A simplified model for the theory of reaction rates near equilibrium has been applied to the reduction of wustite. A linear relationship between the net rate of reaction and the Gibbs free-energy change, ?F, is predicted. The reduction of wustite in H2 -H2O gas mixtures was studied with a microbalance technique at temperatures from 850° to 950 °C. The predicted model was found to be valid to -?F/RT = 0.1 or approximately -200 cal per mole away from equilibrium. ThE theory of reaction rates near equilibrium has been developed by a number of authors. Prigogine, Outer, and Herbo1 have studied the catalytic hydrogena tion of benzene in an attempt to deduce some intrinsic connection between reaction rates near equilibrium and thermodynamics. Manes, Hofer, and weller2 have derived more general expressions for reaction rates near equilibrium from classical thermodynamics. Hollingsworth3,4 has commented briefly on the work of Manes et al. Benson5 has summarized in a general way the results of the earlier contributions. It is the purpose of this paper to apply the theory of reaction rates near equilibrium specifically to the reduction of wustite in H2-H2O gas mixtures. The basic premise is that the reduction of wustite proceeds by a surface reaction, rather than by solid-state diffusion ,or gaseous diffusion. Richardson and Dancy6 and Gellner and Richardson7 have suggested that the reduction of wustite may be governed by iron diffusion in wustite. Mckewan8-11 has proposed that reduced iron layers on various oxides are sufficiently porous to offer a negligible impedance to the reducing gas. The linear motion of interfaces reported by McKewan and discussed by Themelis and Gauvin12 indicates the lack of diffusive control during reduction. The reduction studies of magnetite reported by Quets, Wadsworth, and Lewis13 give additional evidence that reduction rates are linear when the reaction products are porous and nonprotective. The interpretation of measurements reported in this paper is predicated upon a surface-controlled reduction reaction, at least in the earliest stages of reduction when the reduced iron layer is thin.

Jan 1, 1967

By J. Chipman, J. C. Fulton

Reduction of silicon from blast-furnace-type slags by carbon-saturated iron is a very slow reaction even under conditions of rapid stirring. Equilibrium under atmospheric pressure of carbon monoxide was approached from both sides, and the silica-silicon relation was established at temperatures of 1425º to 1700°C for slags containing up to 20 pct Al2O3. Silicon carbide is formed by reaction of graphite with high silica slags and the conditions for its formation were determined. Activities of SiO2 and of CaO in their binary solutions at 1600°C were determined. The effects on the activity of SiO2 were established for additions of 10 to 20 pct AI2O3 and of 10 pct MgO. STUDIES of chemical reactions between blast-*>-5 furnace slags and metal have been focussed on the transfer of sulphur from metal to slag. The important role which silica reduction plays in this process' has led to a study of the transfer of silicon from slag to metal and the equilibrium represented by the equation SiO2 (in slag) + 2C (graphite) = Si + 2CO (g). [I.] The authors2 have published an account of the experimental method employed in attacking this problem and of three series of experimental results at 1600°C. This paper contains data on some additional compositions and extends the observations to cover the temperature range 1425° to 1700°C. The data are used to determine the activity of silica in the slags. As in the earlier experiments, the atmosphere was carbon monoxide which flowed through the furnace at 150 ml per min. In certain heats designated in the tables and figures, the gas was bubbled through the melt using a graphite tube. The latter increased in porosity during a run and in some cases bubbling ceased as indicated by cessation of surging. Some results were discarded for this reason. Experimental Results The new data are shown in Tables I through V and both old and new data are plotted in Figs. 1

Jan 1, 1955

By E. B. Swanson

Frequent reference has been made to the increased domestic gasoline demand recorded for 1931. This increase was in the neighborhood of 7,000,000 bbl. Although smaller relatively than that to which the oil industry had become accustomed by virtue of the experience of preceding years, the increase was of substantial amount, particularly at a time when any increase at all could be regarded with eminent satisfaction. Less has been said, however, of the 18,000,000 bbl. decline in gasoline shipments to territories and foreign countries. When the loss of business outside the United States is combined with the domestic increase, there results a net loss of some 11,000,000 bbl. in total gasoline demand. The gain of 2 per cent in domestic sales gives way to a loss of 2.5 per cent in total domestic and foreign sales. The United States actually has been losing ground in the international gasoline market since 1924, when shipments from this country equaled 72 per cent of the gasoline shipments from the leading gasoline-producing countries of the world. A loss in relative standing was recorded with each succeeding year. As long, however, as gasoline shipments showed an actual increase, the loss in relative standing was of little concern. Foreign producing centers annually supplied an increasing share of the foreign gasoline markets, but, until the past year, the demand abroad continued to increase at a pace which could accommodate all of the increased output of foreign plants and yet require increasing quantities from the United States. It was not until 1931 that the various factors were combined so as to produce an actual and substantial decrease in the foreign demand for United States gasoline. Consumption in foreign countries generally declined, while the output of foreign refineries and the foreign manufacture of substitute fuels continued to increase. From our own viewpoint, this meant a loss of some 18,000,000 bbl. of gasoline business in foreign countries, one-half of it probably due to the lowering in foreign demand and the other half to the increased output of foreign refineries and the increased utilization of substitute fuels.

Jan 1, 1932

By C. W. Mason

TIN has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphur. The notorious "tin disease," which Cohen1 has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white 0 tin to cubic gray a tin, has apparently encouraged the expectation that one or more addi-tional polymorphic modifications might exist. The search for confirma-tion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but for previous assumptions. The ball apparently was started rolling in 1880 by Trechmann,' who reported a new modification of tin (y tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be y tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller.3 Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,6 by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) and stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencer3 in 1921 examined the above evidence critically; he found similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on a second lot of crystals, not described crystallographically.)

Jan 1, 1939