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By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.' Also, tantalum in combination with rhodium,' iridium,' or platinum' stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By Charles H. Thurman

The data given herein were first included in a paper read before San Francisco Section, A.I.M.E., in October 1940, and are applicable to conditions existing until the gold-dredging industry was temporarily suspended by Order L-208 of the War Production Board in the fall of 1942. There is no doubt that gold dredging will be resumed at some future time, and on a scale equivalent to that of the recent past, but the cost data given herein will be affected to some extent by conditions existing at that time, and by labor rates and prices for materials then prevailing. Dragline vs. Bucket-line Dragline dredges should not be considered for mining large areas of low-grade placer gravel. In such deposits a dragline operator with a 5-cu. yd. dragline would be doing well to maintain an operating cost of 6¢ per cu. yd., while a bucket-line dredge with buckets no smaller than 7 cu. ft. each could be operated for less than 4¢ per cu. yd. By operating costs, I mean only field charges such as direct operating and overhead, which includes pay roll, power or fuel, repairs and maintenance, insurance, land clearing and general expenses, but not including such items as prospecting, depletion, depreciation of equipment, State Franchise Tax, or Federal Income Tax. It is not to be inferred that a dragline dredge cannot make a profit in small low-grade deposits, where the extent of a given property is too small to justify the use of the more costly bucket-line dredge. Consider small deposits of 106 gravel. It is obvious that a deposit of 5,000,000 cu. yd. of such gravel could not be mined profitably with a new 7-cu. ft, bucket-line dredge, costing upward of $250,000, and in operation costs at 4¢ per cu. yd., paying for land or royalties out of earnings; nor could a new combination 5-cu. yd. dragline and washing plant, worth upward of $125,000 and working at 6¢ Per cu. yd., make a profit. These comparisons are made because the hourly capacity of both types of dredges is nearly the same. The bucket-line dredge averages 93 per cent operating time in 24 hr., as against about 80 per cent or less for the dragline dredge. These Percentages of operating time are important factors in making a comparison of this kind- The bucket-line dredge has greater efficiency in cleaning soft bedrock, usually characteristic of dredging deposits, and a 7-cu. ft. bucket-line dredge can be efficient to a total digging depth of 80 ft- (65 ft. below water, 15 ft. above). A 5-cu. Yd. dragline dredge is limited to about 30 ft. of efficient digging depth, 5 ft. of which could be above water. In small areas of gravel not over 30 ft. deep, a 5-cu. yd. dragline dredge could make a profit where a bucket-line dredge could not do so. As an example: compare the dredging of 3,000,000 cu. yd. of 10 gravel 28 ft. deep with bucket line, costin 4¢ Per cu. yd., and with a 5-cu. yd. dragline dredge operating at 6¢ Per cu. yd. Because of small yardage, new equipment is not warranted, therefore we can assume that the dredges of both types are used equip-ment, fully depreciated. Dismantling, mov-

Jan 1, 1946

By Charles H. Thurman

THE data given herein were first included in a paper read before San Francisco Section, A.I.M.E., in October 1940, and are applicable to conditions existing until the gold-dredging industry was temporarily suspended by Order L-208 of the War Production Board in the fall of 1942. There is no doubt that gold dredging will be resumed at some future time, and on a scale equivalent to that of the recent past, but the cost data given herein will be affected to some extent by conditions existing at that time, and by labor rates and prices for materials then prevailing. DRAGLINE VS. BUCKET-LINE Dragline dredges should not be considered for mining large areas of low-grade placer gravel. In such deposits a dragline operator with a 5-cu. yd. dragline would be doing well to maintain an operating cost of 6¢ per cu. yd., while a bucket-line dredge with buckets no smaller than 7 cu. ft. each could be operated for less than 4¢ per cu. yd. By operating costs, I mean only field charges such as direct operating and overhead, which includes pay roll, power or fuel, repairs and maintenance, insurance, land clearing and general expenses, but not including such items as prospecting, depletion, depreciation of equipment, State Franchise Tax, or Federal Income Tax. It is not to be inferred that a dragline dredge cannot make a profit in small low-grade deposits, where the extent of a given property is too small to justify the use of the more costly bucket-line dredge. Consider small deposits of 10¢ gravel. It is obvious that a deposit of 5,000,000 cu. yd. of such gravel could not be mined profitably with a new, 7-cu. ft. bucket-line dredge, costing upward of $250,000, and with operation costs at 4¢ per cu. yd., paying for land or royalties out of earnings; nor could a new combination 5-cu. yd. dragline and washing plant, worth upward of $125,000 and working at 6¢ per cu. yd., make a profit. These comparisons are made because the hourly capacity of both types of dredges is nearly the same. The bucket-line dredge averages 93 per cent operating time in 24 hr., as against about 80 per cent or less for the dragline dredge. These percentages of operating time are important factors in making a comparison of this kind. The bucket-line dredge has greater efficiency in cleaning soft bedrock, usually characteristic of dredging deposits, and a 7-cu. ft. bucket-line dredge can be efficient to a total digging depth of 80 ft. (65 ft. below water, 15 ft. above). A 5-cu. yd. dragline dredge is limited to about 30 ft. of efficient digging depth, 5 ft. of which could be above water. In small areas of gravel not over 30 ft. deep, a 5-cu. yd. dragline dredge could make a profit where a bucket-line dredge could not do so. As an example: compare the dredging of 3,000,000 cu. yd. of 10¢ gravel 28 ft. deep with bucket line, costing 4¢ per cu. yd., and with a 5-cu. yd. dragline dredge operating at 6¢ per cu. yd. Because of small yardage, new equipment is not warranted, therefore we can assume that the dredges of both types are used equipment, fully depreciated. Dismantling, mov-

Jan 1, 1945

By Lovell Lawrence

MAGNETITE deposits in the Eastern States have been mined uninterruptedly since pre-Revolutionary War days. The industry, thriving in normal times, was given impetus in all periods of tumult, and continued to advance and expand, until the Lake Superior ores came into production. A period of comparative quiet existed until increased freight rates, together with increased mining costs on Lake Region ores, permitted the magnetites again to compete. This, coupled with World War demands, created unpre¬cedented activity. Producing plants were at their peak, new mines were equipped and put in operation and the industry pushed production beyond the absorption point. Ore stocks were tremendous, internal competition severe, and a great increase in import of European ores brought the industry to a low ebb in 1923.

Jan 1, 1933

By Harry L. McNeill

THE Selective Media Process was developed by the author in a laboratory provided by The Steårns-Roger Manufacturing Co. It is the outcome of an [ ] investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Cliffs Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7 ½ -hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼ -hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7 ½ -hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). When treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is fed to the washing plant the coarse

Jan 1, 1946

By Harold Cook

Discussion of the paper of HAROLD EARLE COOK, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 375 to 400. ALBERT SAUVEUR, Cambridge, Mass.-I think we must all agree with Lieutenant-Commander Cook when he says that there is a great deal of room for improvement in the annealing of steel castings and that better results would be attained if the annealing were conducted in closer agreement with scientific requirements. Whether even a carefully annealed steel casting can ever be made the equal of a steel forging of good quality is still a debatable question. Nevertheless, we all realize that very greatly improved results can be attained by careful annealing. Lieutenant-Commander Cook refers to some requirements calling for annealing steel castings above the Ac1 point. He is undoubtedly right where he says that this should be the Ac3 point. Take, for example, a steel casting containing, say, 0.35 per cent. of carbon, having a very coarse structure made up of coarsely crystalline ferrite. If this is heated just above the Ac1 point the ferrite remains, of course, just as it was before, while the pearlite is converted into a solid solution, austenite. Upon cooling, all this austenite is again converted into pearlite, or sorbite, while the coarse structure of the ferrite remains unchanged and the annealing has accomplished very little. It is therefore surprising that the requirement of annealing above the Ac1 point should appear, in these specifications.

Jan 5, 1916

By A. Eilers

ALTHOUGH the process to which I refer in this paper has been in successful operation for nearly five years, during which time it has been introduced, superseding all other processes having in view the same end, in almost every lead refinery in the country, no description of it, giving economical data, has ever appeared in print, nor has the process been known in its details to any considerable number of engineers beside those conducting it at their works. A discussion of this subject at the present time becomes especially interesting in view of a late publication in the Prussian ministerial organ for Mining and Metallurgy, by Dr. Wedding, in which the method of treating the zinc-silver-lead alloy by distillation, as finally settled upon at Tarnowitz, is very minutely and fully described. It is the more interesting, because in that article reference is made to the American method in an unfavorable light, while, at the same time, it is clear from the article itself, that the most important details of the process, besides the one that it is conducted in black-lead retorts, were not at all understood. In publishing herewith the details of our American method, one of my objects is to invite comparisons between our simple and direct process and the elaborate one at Tarnowitz. In extracting the silver from work-lead by means of zinc, it is always the intention, in this country, to obtain a zinc-crust so rich in silver that the rich lead resulting from subsequent distillation

Jan 1, 1875

By Harry L. McNeill

The Selective Media Process was developed by the author in a laboratory provided by The Steams-Roger Manufacturing Co. It is the outcome of an investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Clifis Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7½-hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼-hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7½-hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). when treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is led to the washing plant the coarse

Jan 1, 1947

By Harry L. McNeill

The Selective Media Process was developed by the author in a laboratory provided by The Steams-Roger Manufacturing Co. It is the outcome of an investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Clifis Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7½-hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼-hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7½-hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). when treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is led to the washing plant the coarse

Jan 1, 1947

Professor Somasundaran has given an excellent presentation of the numerous problems which remain to be solved before the selective aggregation of fine particulates is likely to see broad commercial application in the beneficiation of mineral fines. However it is useful, I think, to reiterate some of the major problem areas. The over-riding factor which has limited the development of selective aggregation techniques is that processes such as coagulation and flocculation tend to be inherently non-selective. Conditions which favor the aggregation of one kind of fine particles usually favor the aggregation of all kinds of particles. As Professor Somasundaran has pointed out, the state of aggregation of a fine-particle dispersion is primarily determined by the forces of interaction between the individual particles. In most systems, the dominant forces are: 1. van der Waals - London Dispersion forces between the particles themselves 2. electrical double layer forces 3. steric forces between adsorbed layers on the surfaces of the particles. The London Dispersion forces between like particles are always attractive, but for dissimilar particles dispersed in a fluid medium can, in some cases, lead to a net repulsion. Electrical double layer forces always lead to repulsion between like particles but can, again, cause either attraction or repulsion for dissimilar materials. The steric forces, which are by far the least understood of the three types, can also lead to attraction or repulsion depending on condi-

Jan 1, 1979

In the history of American mining, so far as I know, there is no cleaner, brighter, or more completely successful mining adventure than that of the United Verde Extension.* It deserves to be placed on record here. The mine is at Jerome, 25 miles northeast of Prescott, in Yavapai county, Arizona. For 30 years before the U.V.X., as it is known to mining men, achieved celebrity, the Jerome district was identified with a copper mine, the United Verde, one of the great mines of the world. The success of this mine, of course, stimulated the search for similar orebodies, or for an extension of those already known, in adjacent ground; but, despite vigorous prospecting, the United Verde remained for many years alone in its glory. The reason for this solitariness was geologic: a fault with a big throw frustrated the effort to trace the ore-zone, thereby causing exploratory work to be both uncertain and costly. Despite these failures to develop other mines in the vicinity, the belief persisted that all the ore was not localized in the United Verde mine, but before we consider the reasons for such a belief we must look at the geologic conditions. The basal rock of the Jerome district is a schist, which has been correlated with the Yavapai formation of the Bradshaw quadrangle. This schist is geologically ancient, for it is of pre-Cambrian age. It is composed of volcanic tuffs, together with sediments, both argillaceous and siliceous, all of which

Jan 1, 1932

By H. C. Fiedler

X HE development of the cube-on edge secondary re-crystallization texture in Si-Fe strip requires that normal grain growth be restrained. It has been shown that the degree of restraint and hence the completeness of secondary recrystallization depends upon the size and number of second-phase particles, which in turn is dependent upon the prior processing history.1y2 The purpose of this note is to show that, for heats in which manganese sulfide particles are providing the restraint to grain growth, the choice of hot rolling temperature depends upon the manganese content. The making and processing of the heats to the final gage of 0.012 in. has been described.3 The compositions are given in Table I. Apparent in Fig. 1 is the decrease in the ability of strips hot-rolled from 1175°C to undergo secondary recrystallization as the manganese content increases. It has been shown that 1175°C is below the solubility temperature of 0.014 pet S in even the 0.038 pct Mn alloy: and the observed behavior is attributed to an increasing fraction of the sulfur forming large manganese sulfide particles at the heating temperature for hot rolling. This fraction of the sulfur is thus unavailable to subsequently form the small, uniformly dispersed particles which are needed to restrain normal grain growth. Since the sulfur is completely in solution at 1325°C,3 strips from all three alloys show strong secondary recrystallization behavior when hot-rolled from that temperature.

Jan 1, 1969

By H. B. Charmbury, D. R. Mitchell

Recovery of fine coal from solids reporting to wash water has become increasingly important. These solids range from about 28 mesh to 0 and constitute 3 to 7 pct by weight of the feed tonnage to a coal preparation plant. In the past they were usually wasted to streams, but present clean stream legislation makes it necessary to remove them from the wash water and, if economically possible, recover the associated coal as a saleable product. Where these solids are not wasted to streams or to slime ponds they are recovered by thickeners and filters. Since filter cake is often high in ash or sulfur, or both, it is not readily marketed or used. Common practice is to mix it with other plant products, generally slack or cleaned run-of-mine. Uniform blending is difficult, not only because the impurity is usually high, but also because during certain operating periods it is possible to get a concentration of this filter cake in a railroad or barge. At some plants filter cake has been derived from the froth flotation clean-up of Dorr thickener underflow. The operating circuits required for a froth flotation plant make this a comparatively high-cost treatment, and in the last few years experiments have been carried out with bulk oil methods. These also are quite expensive and lend themselves only to special situations. Table I gives some characteristics of thickener underflows for plants in the Pittsburgh area treating Pittsburgh seam coal. It will be noted that there is a concentration of impurities in the -200 mesh sizes.

Jan 1, 1960

By David Sinclair, Philip B. Bucky

THE dimensions and shapes of mine structures may at present be determined by (1) field experience, (2) structural calculations, and (3) barodynamic tests.§ None of these, however, provide information as to the stresses, their direction and distribution in a mine structure. For the design of pillars, the placing of openings relative to working places such as gangways, haulage levels, etc., this information is desirable. Photoelastic methods provide this and, while relatively new, their application in all engineering fields is assuming increasing importance. This paper, therefore, will present the method with a few applications to mining, and with sufficient reference for further study by the reader. PART I THE PHOTOELASTIC METHOD The photoelastic method of stress measurement determines the stress distribution in a two-dimensional model by optical means. It makes use of the fact that when a piece of isotropic transparent material, such as glass, celluloid, or Bakelite, is stressed and viewed in polarized** light a picture is seen which indicates by its color bands of light, or fringes, the magnitude of the stresses, their direction and their distribution. GENERAL EXPLANATION The stress at any point 0 in a structure (Fig. 1), may be resolved into two components, P and Q, each a pure tension or compression, at right angles to each other, called principal stresses.1 To fully identify the stress, the values of P and Q and their directions or angle [0] must be known.

Jan 1, 1940

COLUMBIA SECTION STANLY A. EASTON, Chairman, FREDERIC KEFFER, Vice-Chairman, L. K. ARMSTRONG, Secretary-Treasurer, P. 0. Drawer 2154, Spokane, Wash. D. C. LIVINGSTON FRANK A. Ross The first meeting of the Columbia Section was held on March 24, as a part of the 1916 Northwest Mining Convention which was held under the -auspices of the Spokane Mining Men's Club assisted by the Spokane Chamber of Commerce, the technical program being in charge of the Spokane Engineering and Technical Association assisted by the local sections of the A. I. E. E., A. S. C. E., and A. I. M. E. The program of the successive sessions was carefully arranged with view to its application to mining, and in addition to the technical program there were exhibits of ores, minerals, devices, etc., of interest to the delegates, who numbered over 500. A portion of the program was also arranged with special reference to the requirements of the prospector and miner. A reception, a banquet, a complimentary luncheon, a regular daily call' of the Stock Exchange, a visit to the High Schools and to one of the substations of the Washington Water Power Company and to the Union Iron Works kept the visitors entertained, the ladies being looked after by a special committee of ladies who held open house during the entire week. Several important resolutions were passed by the Convention and one by the Columbia Section, A. 1. M. E. With Stanly A. Easton, chairman, presiding, the Columbia Section, American Institute of Mining Engineers, occupied the time between 2.00 and 5.30 p.m., March 24th, the Moorish room of the Spokane hotel being filled with members and their guests. "The Apex Law and the Mineral Surveyor" was a paper presented by F. W. Callaway and generally dis-cussed because of its local application in the Coeur d'Alenes, the conclusions being reached after expensive litigation between two of the large mining operators in that district.

Jan 6, 1916

By W. E. Horst

Flotation feed was hell constant for batch laboratory tests and continuous pilot and commercial plant tests on a spodumene ore to determine the relation.ship between flotation behavior and the size and type of flotation machine. Results. showed that additional retention time would be needed in the plant flotation circuit to duplicate laboratory or pilot plant performance when operating Dariables of the. plant flotation machines remained unchanged. During the past few years of operation at Kings Mountain, N. C., full-scale flotation has generally yielded poorer metallurgical results than those obtained in the laboratory or pilot plant. After 2 min in each size of Denver flotation machine in the spodumene rougher circuit, pilot recovery (41.7 pct) was almost three times that of the plant (13.6 pct) and about twice that of the laboratory (21.0 pct). Pilot and commercial plant data are based on continuous operation, and laboratory results on batch testing of rougher performance. The ore is a pegmatite containing spodumene, feldspar, quartz, mica, and amphibolite. Data were accumulated to evaluate the scale-up relationships between laboratory, pilot plant, and plant flotation cells. Flotation rate constants and dimensional analysis were used to define the relationship existing between flotation behavior and scale of operation. Measuring Flotation Rates: Efficiency of the rougher stage was measured by flotation rate, defined as the recovery that can be attained within a given time." • The problem of measuring flotation rates has been studied by many investigators, whose methods have varied. Published studies an flotation kinetics have been summarized recently by Gaudin.l When comparing flotation rates, it is more satisfactory to compare straight line relationships between recovery and flotation time than exponential curves resulting from plotting cumulative recovery vs cumulative flotation time. To convert the exponential curves into straight line relationships, rate equations were applied similar to those used in chemical kinetics to study the velocity of chemical reactions. Two rate equations have been used in this investigation to measure efficiency of the various cells: 1.5 order Rate Equation dR/dt=k (A-R)1.0 [Eq.1] Second Order Rate Equation dR ---- - K(A - R)2 [Eq. 2] dt Upon integration Eq. 1 becomes 1/(A-R)1/2=k/2 t+1/A1/2 [Eq. 3] and Eq 2 becomes: or fEq. 4] t/R=1/A2K+t/A [Eq. 4] where R = cumulative recovery [percent recovery of total value (spodumene) in flotation feed]. A = initial concentration, pct (100 pct of mineral to be separated). t = flotation time (minutes). k = flotation rate constant for 1.5 order rate equation [units: 1/(percent) 0.5 (min)1. K = flotation rate constant for second order rate equation [units: 1/(percent) (min) 1.

Jan 1, 1959

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By Joseph L. Gillson

Bentonite, designating a distinct type of clay, is a young name in mineral nomenclature in the light of the age-old names of most other useful nonmetallics. The earliest references in literature are to "soap clay" (1873) "taylorite" (1888) and finally "bentonite" in 1897, from its occurrence in the Fort Benton series of rocks near Rock Creek, Albany County, Wyoming. Bentonite is a rock term and consists largely of montmorillonite clay. The latter name was proposed in 1847 for a plastic clay found at Montmorillon, France. A clay of apparently identical properties was described by Cronstedt of Sweden in 1788 and a number of other similar clays found in France were given other names in publications from 1853 to 1856. The mineral name montmorillonite was recognized by Dana in 1892. The recognition of "clay mineral" distinctions which led to the present-day classifications of clays by their chief mineral content, dawned in the early part of the twentieth century. Grim6 has aptly said: About 1924, Ross10 and some colleagues of the U. S. Geological Survey began a study of the mineral composition of clays that led to a series of monumental papers on the subject. By the early 1930's what has come to be known as the clay-mineral concept became firmly established in the minds of a great many people actively studying clay materials. The clay mineral concept designates the major clays as kaolins, montmorillonites and illites and by this concept bentonites are now defined as "fine-grained clays containing not less than 85 pct montmorillonite" and a wide variety of clays found all over the world are included in that classification. They could all properly be called "montmorillonite clays" but the common commercial name is bentonite. For a period of over forty years from the time of the earlier discoveries, bentonite was thought to be only the sodium type highswelling clay produced principally in Wyoming. By the clay mineral concept, non-swelling montmorillonite clays also became known as bentonite. In the trade there are two broad divisions-sodium bentonite, often called Wyoming or "western," which expands in water and carries sodium as its predominant exchangeable ion, and calcium bentonite often called "southern," which has negligible swelling and carries calcium as its principal exchangeable ion. There are many intermediate gradations. Properties The mineralogy and chemistry of the clays are so complex that the subject cannot be summarized briefly. The reader is referred to Chapter 12 of this volume in which the subject is treated at some length. Grim6 gave the formula for montmorillonite as (OH)4Si8AL4020.nH2O. He wrote: Montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. . . . Exchangeable rations occur between the silicate layers. . . . The words "tetrahedral" and "octahedral" refer to the coordination number of the cations in the unit cell in the crystallographic lattice. Carroll5a stated: That the montmorillonite structure is the same as that of mica, but the layers are not held together by K+ ions; and water and other polar molecules, such as organic molecules, can enter between the unit layers and cause expansion. Ex-

Jan 1, 1960

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-' have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

By E. E. Wark, J. Rogers, I. W. Wark, K. L. Sutherland

SOAPS have been used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xanthates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present eminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies.[t] A broad, semi quantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. THE PARAFFIN CHAIN SALTS The basic requirements for a "collector" in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polarnonpolar compounds is the paraffin chain salts: CH3(CH2) „X where X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -CO2Na, -SO3Na, -SO4Na, - PO4Na2, or an aminonitrogen group, the

Jan 1, 1946