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By Clarence Zener

Theoretical considerations by one of the authors have ledl to the prediction that the dynamic internal friction of annealed metals has a broad maximum at a certain grain size. This prediction they have verified2 for alpha brass. In the present paper the theory is extended to include the precise manner in which the internal friction varies with grain size on either side of the maximum. New experimental data are presented to test this extended theory. The physical basis for the type of internal friction that is being investigated lies in the interplay between stress and temperature. Just as local fluctuations in temperature give rise to local fluctuations in stress, so likewise fluctuations in stress give rise to fluctuations in temperature. But temperature gradients give rise to necessarily irreversible thermal currents, and hence to internal friction. The theory for this type of internal friction has been developed quantitatively,³ and has been experimentally verified,4,5 for the particularly simple case of the transverse thermal currents accompanying transverse vibrations. Of more fundamental importance are the intercrystalline thermal currents accompanying all types of vibration. The variation in stress across grain boundaries arises from the elastic anisotropy and at least partial random orientation of the individual crystallites. An exact quantitative treatment of the internal friction due to these thermal currents is of course out of the question. However, much information can be obtained from general arguments.1,6 Thus when the frequency of vibration f is low, or when the grain size d is small, adjacent grains remain nearly in thermal equilibrium, and vibration proceeds isothermally with little internal friction. Again, when the frequency is high, or the grain size large, the heat flow per cycle is small, the vibration proceeds adiabatically with little internal friction. The internal friction will become a maximum in the transition region. The degree of adiabatic-

Jan 1, 1940

By Clarence Zener

Theoretical considerations by one of the authors have ledl to the prediction that the dynamic internal friction of annealed metals has a broad maximum at a certain grain size. This prediction they have verified2 for alpha brass. In the present paper the theory is extended to include the precise manner in which the internal friction varies with grain size on either side of the maximum. New experimental data are presented to test this extended theory. The physical basis for the type of internal friction that is being investigated lies in the interplay between stress and temperature. Just as local fluctuations in temperature give rise to local fluctuations in stress, so likewise fluctuations in stress give rise to fluctuations in temperature. But temperature gradients give rise to necessarily irreversible thermal currents, and hence to internal friction. The theory for this type of internal friction has been developed quantitatively,³ and has been experimentally verified,4,5 for the particularly simple case of the transverse thermal currents accompanying transverse vibrations. Of more fundamental importance are the intercrystalline thermal currents accompanying all types of vibration. The variation in stress across grain boundaries arises from the elastic anisotropy and at least partial random orientation of the individual crystallites. An exact quantitative treatment of the internal friction due to these thermal currents is of course out of the question. However, much information can be obtained from general arguments.1,6 Thus when the frequency of vibration f is low, or when the grain size d is small, adjacent grains remain nearly in thermal equilibrium, and vibration proceeds isothermally with little internal friction. Again, when the frequency is high, or the grain size large, the heat flow per cycle is small, the vibration proceeds adiabatically with little internal friction. The internal friction will become a maximum in the transition region. The degree of adiabatic-

Jan 1, 1940

By D. R. Walker, M. C. Shaw

THE laws of comminution of Kick and Rittinger have been debated for many years. Certain data obtained from ball mill and drop tests are found to be in approximate agreement with Rittinger's law while other data would seem to support Kick's law. In all these tests the energy required to produce a wide variety of particle sizes has been studied. Surface area has also been measured with considerable difficulty, at first because it was thought that the energy associated with crushing was that required to create new surface, later because of precedent and because a more fundamental variable was unknown. Tests made with the machine shop type of grinding process show that normally brittle materials that are usually crushed can behave like the more ductile metals. Brittleness is then a relative property largely dependent on specimen size and stress state. The machine grinding operation offers a convenient means for studying the comminution of materials in which the important size variable retains its identity. The energy required to grind a certain volume of material is shown to be strongly de- pendent on size. Kick's law is found to hold very well for particles below 1 micron in size, while Rittinger's law holds approximately in the comminution of larger particles. While a physical origin of Kick's law is established in terms of the theoretical strength of materials having a perfect lattice structure, there is found to be no physical basis for Rittinger's law.

Jan 3, 1954

By Oswald J. Heinrich

During the last twenty years much has been done to investigate and define the Mesozoic formatibn of the United States along the Atlantic States, as well as in' the Territories. The investigations of Professors Hitchcock, Emmons, Hayden, H. D. Rogers, and those now in progress in connection with the geologicd surveys of Penn-

Jan 1, 1879

By W. S. Steele

Vermiculite is a nonmetallic mineral of the mica family, probably related to biotite mica. Its occurrence has been noted at numerous places in the United States and in some foreign countries, but it can be said that vermiculite is of only moderately wide distribution. A laboratory and field survey of over 60 deposits in the United States by F. 1;. Schundler & Co., of Joliet, Ill., indicates that the purest deposit represented in this survey is on the property of the Zonolite Company at Libby, Montana The Zonolite Company is commercially active and the vermiculite it produces is sold as Zonolite. Hereafter, in this report, the word "Zonolite " will be used to designate the vermiculite produced by the Zonolite Company. Values given herein to Zonolite are peculiar to the vermiculite produced from the Zonolite Company's deposits. References to " vermicullite," are to he interpreted as covering the broad field covered by the Schundler survey. Composition and Characteristics of Vermiculite Vermiculite is an aluminum-nmgnesium silicate. The following typical analysis is published by the United States Bureau of Standards: silica, 41 per cent; iron oxide, 7; aluminum oxide, 18; magnesium oxide, 21; calcium oxide, 1; alkalis (sodium and potassium), 1; moisture, 11. Vermiculite breaks down into platelike formation in crushing and grinding operations. Its cleavage is basal. Crude, screened, dry Zonolit,e weighs between 80 and 90 Ib. per cubic foot; its specific gravity is 2.8 and its specific heat is approximately 2. The fusion point of Zonolit'e is 2462" F. Crude vermiculite contains between 7 and 9 per cent of chemically combined moisture. The instantaneous introduction of crude Zonolite into an expansion furnace at a temperature of between 1800" and 2000" F. transforms the combined moisture into steam, which in an effort to liberate itself forces all explosive expansion of the platelike crude material

Jan 1, 1934

By W. W. Coffeen, K. E. Doud

A singular mineral extraction and processing operation is conducted by Metal & Thermit Corp. in Hanover County, Va. The mine presently produces aplite rock, rutile and ilmenite. The deposit lies in the piedmont plain about 25 miles northwest of Richmond. It first drew attention as a result of discovery of float rutile on the surface about 1910. About seven years prior to this, Metal & Thermit through a subsidiary. American Rutile Co., had begun producing rutile'and ilmenite from a deposit in Nebon County, near Piney River, where aplite rock and ilmenite are mined today. Because of the interest in titanium minerals and the similarity of the new deposit to the Nelson County deposit, Metal & Thermit became interested and eventually acquired the Hanover County deposit.

Jan 10, 1962

By Will H. Coghill

FLOTATION has been so closely allied with the sulfide minerals and their early and associated oily reagents that the term "oil flotation" has erroneously been applied to the entire flotation process. Today, the term "chemical flotation" might be used to advantage. Flotation literature has dealt primarily with the removal of sulfides. from non-sulfide gangues, and the separation of one sulfide from another.. Now, the application of the process to the separation of nonsulfide minerals is coming to the fore; and from the standpoint of the number of commercial minerals involved, the flotation of nonsulfides offers the larger field. Here, soap or soap-forming substances, such as the fatty acids and their derivatives, are used; hence there may well be a subdivision of the chemical flotation process called "soap flotation." Early experimenters learned that it was easy to form a froth or foam that would carry a part or all of the ore charge over the lip of the flotation machine; but this could not be regarded as flotation because of the lack of selectivity. Doubtless soap was one of the first reagents tried, and doubtless it was rejected on account of its gangue-carrying properties. Now this same gangue-carrying ability makes soap an acceptable reagent, for we are dealing with that, which among sulfides, is considered "gangue." As in the flotation of sulfides, so in the flotation of nonsulfides, the selective flocculation of the mineral and the dispersion of the gangue are the first objectives. In fact, these two phenomena epitomize flotation. They depend upon the unlike surface properties of the respective minerals; and, as long as the components of an ore have unlike surface properties, a separation is possible, at least in theory. Often in nonsulfide flotation it makes little difference which mineral floats and which is depressed; generally only a separation is sought.

Jan 1, 1932

By Barry K. McMahon

The fundamental problem in rock mechanics is accounting for the discontinuous and anisotropic nature of the jointed rock mass. It is this problem that makes rock mechanics distinct from the mechanics of steel, glass, or concrete. Existing mathematical models explain much of the behavior of rock cores in the laboratory but, in civil engineering at least, the rocks that matter are the ones that are already broken. On the other hand, the basically descriptive methods now used in engineering geology do not lend themselves easily to mathematical analysis. A set of indices of geological properties related to the strength and deformation characteristics of jointed rock is needed. Like the index properties used in soil mechanics these will probably not have precise mathematical meaning, but once correlations are established with large scale tests they can form a basis for the transfer of test results, obtained in one area under one set of conditions, to the prediction of rock behavior in another area under another set of conditions. Indices of rock properties are even more important in rock mechanics than in soil mechanics as the cost of testing is much higher. To be useful, these indices must be easily and quickly measured and give reproducible results when measurements are made by different people. In this paper the word "joint" means all naturally occurring rock fractures with less than 3 in. of clay or other soft coating material. EXISTING INDICES OF ROCK PROPERTIES A comprehensive review of indices of rock properties for intact rock is given by Deere and Miller.' They provide charts ". . . for estimating the strength or modulus properties for intact rock from the numerical indices obtained by either the Schmidt hammer, the Shore Scleroscope,

Jan 1, 1968

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By L. M. Barker

THE New Cornelia Branch of the Phelps Dodge Corporation is at Ajo, Pima County, Ariz. It is at the southern terminus of the Tucson, Cornelia and Gila Bend Railroad, which connects with the Southern Pacific Railroad at Gila Bend, Ariz., approximately 43 miles to the north. HISTORY Early history of the Ajo district has been related by A. W. Allen1 and by T. A. Rickard.2 Briefly, steps looking to the large-scale development of the ore body were instituted as early as 1912. This work culminated in the equipment of the property for open-pit mining by steam shovels. Ores initially mined carried economic amounts of copper carbonates as the principal copper-bearing mineral. Treatment methods developed for the extraction of the copper content involved leaching and a 5000-ton leaching plant was constructed and placed in operation in early 1917. Description of methods and equipment employed in this plant has been given by A. A. Tobelmann and James A. Potter.3 As exhaustion of the carbonate ore body neared, and mining oper-ations exposed an adequate tonnage of sulphide ores, a 5000-ton con-centrator was constructed for their treatment. That plant has been described by H. Kenyon Burch.4 Construction was completed and the plant was placed in operation in early 1924. Changes made in the original plant to improve practices and increase production will be the subject of subsequent paragraphs of this paper.

Jan 1, 1939

By H. K. Martin

IN September 1954 the Lavender pit concentrator at Lowell, Ariz., began treating low grade porphyry copper ore from the nearby Lavender mine. Nominal capacity of the mill is 12,000 tpd, but production now averages 16,226 tpd. Plant design was somewhat affected by the re-use of old equipment and the substantial re-use of old buildings. A breaking-in period between June 24 and Sept. 1, 1954, was devoted to training operators and making minor changes in launders, chutes, and piping. From Sept. 1, 1954, to July 1, 1956, the mill treated 8,598,105 dry tons of ore, from which 556,541 tons of concentrate were produced, containing an indicated 144,055,185 lb of copper.

Jan 11, 1957

By J. I. Budnick, W. B. Ittner III, D. P. Seraphim

A reliable technique has been developed for producing single crystals of tantalum in the form of small diameter wires. By suitably heat treating these and polycrystal samples, first in an oxygen atmosphere and finally in vacuum, it has been found possible to reduce residual resistivities to 10-3 microhm-cm. The purity of these samples is thus comparable to the purities obtained in zone-refined silver, copper, and aluminum. THE growth and purification of pure single crystals of the transition metals is, in general, difficult. The high melting and annealing temperatures of these metals make it necessary to employ rather special techniques in any crystallization process. In addition, the transition metals show a great affinity for and are easily contaminated by nitrogen, oxygen, and carbon. Recently, however. a number of investigators have been successful in growing,

Jan 1, 1961

By George E. Cole

While many parts of Canada's pre-Cambrian shield are well served by railway, it is frequently necessary for prospecting purposes to proceed farther into areas inaccessible by rail. To such areas in summer the canoe was at one time the accepted means of travel for the prospector while the dog team was much used in winter. Although summer travel was much improved by the development of the outboard motor, the lack of facilities for cheap transportation has been a serious hindrance to the employment of capital in opening up the distant fields. The pre-Cambrian surface of Manitoba, like that of Ontario, is hummocky, with rounded hills and ridges of rock alternating with basinlike depressions and valleys occupied by lakes and rivers Or by many low-lying portions covered with muskeg' Routes to the mines have not usually been direct or easy and seasonal vagaries have presented problems in themselves. In summer, water transportation may be the cheapest method for the longer distances but it is not every water route that will satisfy the conditions of loading freight on to a boat or scow and of conveying it without interruption to its destination. By its location, a mine may require a large program of boat transportation in summer Over part of its route, to be followed by winter freighting for the remainder. In order to carry on development and produc- tion over a long period, it may be necessary to haul large quantities of supplies during the winter. This seasonal problem, particularly for the out-of-the-way properties, is SO important and demanding as to make it a major operation in the life of the mine. The -use of the tractor during winter months for heavy machinery and bulk supplies, and the use of the airplane throughout the year for the transportation of personnel and for emergency requirements, have greatly improved transportation to places that are inaccessible by rail. Canada has pioneered in both these methods. Development oF Transportation Twenty-two years have seen a marked change in transportation methods in Canada's mining country. Horse-drawn sleighs have given way to the tractor and that to some extent has been supplanted by the airplane. One of the earliest ventures involving transportation of considerable magnitude was that of the Mandy mine, on Schist at in northern Manitoba. According to accounts of early mining activities in Manitoba, the Mandy mine, beginning December 1916, had 3300 tons of ore hauled 40 miles by sleigh to Saskatchewan River and in summer this was conveyed by barge to The Pas, 130 miles, and then by railroad to Trail, British Columbia, 1200 miles. The mine shipped 6000 tons of ore in 1918 and 15,000 tons in 1919. In winter of the latter year, as many as 300 teams of horses were used on the 40-mile stretch to

Jan 1, 1943

By George E. Cole

While many parts of Canada's pre-Cambrian shield are well served by railway, it is frequently necessary for prospecting purposes to proceed farther into areas inaccessible by rail. To such areas in summer the canoe was at one time the accepted means of travel for the prospector while the dog team was much used in winter. Although summer travel was much improved by the development of the outboard motor, the lack of facilities for cheap transportation has been a serious hindrance to the employment of capital in opening up the distant fields. The pre-Cambrian surface of Manitoba, like that of Ontario, is hummocky, with rounded hills and ridges of rock alternating with basinlike depressions and valleys occupied by lakes and rivers Or by many low-lying portions covered with muskeg' Routes to the mines have not usually been direct or easy and seasonal vagaries have presented problems in themselves. In summer, water transportation may be the cheapest method for the longer distances but it is not every water route that will satisfy the conditions of loading freight on to a boat or scow and of conveying it without interruption to its destination. By its location, a mine may require a large program of boat transportation in summer Over part of its route, to be followed by winter freighting for the remainder. In order to carry on development and produc- tion over a long period, it may be necessary to haul large quantities of supplies during the winter. This seasonal problem, particularly for the out-of-the-way properties, is SO important and demanding as to make it a major operation in the life of the mine. The -use of the tractor during winter months for heavy machinery and bulk supplies, and the use of the airplane throughout the year for the transportation of personnel and for emergency requirements, have greatly improved transportation to places that are inaccessible by rail. Canada has pioneered in both these methods. Development oF Transportation Twenty-two years have seen a marked change in transportation methods in Canada's mining country. Horse-drawn sleighs have given way to the tractor and that to some extent has been supplanted by the airplane. One of the earliest ventures involving transportation of considerable magnitude was that of the Mandy mine, on Schist at in northern Manitoba. According to accounts of early mining activities in Manitoba, the Mandy mine, beginning December 1916, had 3300 tons of ore hauled 40 miles by sleigh to Saskatchewan River and in summer this was conveyed by barge to The Pas, 130 miles, and then by railroad to Trail, British Columbia, 1200 miles. The mine shipped 6000 tons of ore in 1918 and 15,000 tons in 1919. In winter of the latter year, as many as 300 teams of horses were used on the 40-mile stretch to

Jan 1, 1943

By H. M. Howe, E. C. Groesbeck

That the quiescence of a liquid while it is solidifying should favor the formation of columnar crystals, normal of the cooling surface, is seen readily on considering the mechanism of solidification. First, each particle of any composite liquid, whether it be an aqueous solution or a molten metal, in solidifying splits up into two parts, different in composition and hence in fusibility. One part is infusible at the existing temperature, and hence solidifies, and in general attaches itself to the inclosing walls of metal which have already solidified; A, Fig. 1. The other part is fusible at the existing temperature and hence remains molten. In the case of carbon steel, the part of each drop which actually solidifies is poorer in carbon than the drop itself was before it began to solidify, and this impoverishment of the solidifying half-drop enriches the other half-drop in carbon, and thus makes it unfreezable at the existing tern- By this mechanism there arises during solidification a "littoral" or shore layer of liquid B, Fig. 1, bathing the already solidified walls, and more fusible than either those walls or the great remaining central mass of liquid or " deep sea " C, from which it separates them. It is essential that we grasp clearly this conception of a fusible littoral molten layer coating the already solidified walls and separating them from the deep sea. Meanwhile heat is flowing rapidly outward through these walls, its escape cooling them, so that if any given particle of the deep sea metal could get past this littoral layer and come into contact with the solid walls, it would in turn solidify, and like its predecessors would split up in solidifying into a less fusible half-drop which would attach itself to those . walls and a more fusible one which would remain molten. Thus we see

Jan 1, 1920

By W. L. Zeigler

The Galena mill of the Callahan Zinc-Lead Co. is of 150 tons daily capacity and is situated at Lake Gulch, 2 miles west of Wallace, Idaho. (Fig. 1. It was constructed during the summer of 1926, work having been started late in June and the plant placed in operation Oct. 15, following.

Jan 1, 1928

By Mark A. Ammon

The two most widely used methods of measuring hardness are the Brinell and the scleroscope. In the Brinell method a hardened steel ball is pressed into the steel under a definite load and the area of the resulting depression is measured. The load in kg. per sq. mm. of the area of the depression is taken as a measure of the hardness. Within certain limits the hardness number so determined is independent of the load or the size of the ball. In the scleroscope method a small weight carrying a diamond point is dropped through a glass tube upon the steel and the amount of rebound is taken as proportional to the hard-' ness. In both methods the scale of hardness is an arbitrary one; however, they agree in a comparative may, that is, a steel showing 50 per cent. increase in hardness by the Brinell test mill show approximately 50 per cent. increase in hardness by the scleroscope test. Yet upon consideration of the two methods it appears that, upon a steel which has been carbonized, this should not be the case ; for the scleroscope method gives almost exclusively the surface-hardness, and the condition of the material below the surface has but a slight bearing upon the hardness number. The results given by the Brinell method should, however, be the exact opposite; for the depth of penetration 'of a ball pressed into the steel would be dependent to a large extent upon the condition of the material below the surface. This is particularly obvious when it is considered that the size of the ball ordinarily used in the Brinell method is 1 cm. (about 8 in.) in diameter under a load of 3,000 kg., while the diamond point of the scleroscope is in the neighborhood of 0.01 in. across, fitted in a hammer of about 0.5 oz. weight and dropping from a height of 10 inches.

Jan 1, 1913

By Zay Jeffries

THE object of the present paper is to enlarge somewhat on the general principles advanced in my discussion 1 of Mathewson and Phillips' article on. The Recrystallization of Cold-Worked Alpha Brass on Annealing.2 It will also serve as an acknowledgment of Prof. Howe's3 most important remarks on my contribution. In this paper the writer has adopted Prof. Howe's suggestion to substitute the term "germinative temperature" for "critical temperature for grain growth." Instead of being an exact or certain temperature it should be considered that the germinative temperature phenomenon exists throughout a small temperature range. Factors Influencing Fast Growth Phenomena The development of grains of macroscopic size at the germinative temperature should be considered the extreme condition of a general rule. When considered in this light it is not strange that the development of these large grains should be the exception and not the rule. The principal factors influencing the operation of the laws of fast growth temperature are as follows: 1. Rate of heating.

Jan 10, 1916

By J. Leja, J. H. Schulman

FROTH flotation is usually effected by the addition of a collector agent and a frothing agent to an aqueous suspension of suitably comminuted mineral ores. The action of collectors is to adsorb onto the surfaces of minerals to be separated, sensitizing them to bubble adherence. The action of frothers has, in the past, been accepted as that of froth formation only, brought about by a lowering of the air/water interfacial tension. Substances capable of producing froth are classed1a,b according to their relative capacities for production of froth-volume and froth stability in the simple frother-water system. The purpose of this paper is to show that the surface active agents acting as frothers become effective only when there is a suitable degree of molecular interaction taking place between collector molecules and frother molecules at the air/water and solid/ water interfaces. Further, the discussion will demonstrate that the actual mechanism of adherence of an air bubble to a suitably collector-coated particle is due to the molecular interaction collector-frother. This leads to the formation of a continuous interfacial film of associated molecules, anchored to the mineral by polar groups of the collector, and enveloping the whole bubble. The tenacity of adhesion mineral-to-bubble results from the strength and the visco-elasticity of this mixed film. Some 20 years ago Christman2 postulated mutual dependence of collector and frother in effecting flotation. This view was, however, strongly opposed by Wark,3 who pointed out that an addition of frother had no effect on the value of contact angle once this was established in the solution of collector. More recent work by Taggart and Hassialis' indicated that the presence of frother, namely, cresol, leads to the immediate establishment of a contact angle on sphalerite, partially coated with xanthate, whereas an air bubble fails to make contact in potassium ethyl xanthate solution alone, even after 60 min induction time. Wrobel5 raws attention to the selectivity of frothers in flotation. Many instances of antagonistic effects of certain mixtures of frothers (or collectors and frothers) on flotation froth have been known to flotation operators and have been reported in literature. Taggart6 and Cooke7 give several examples of incompatibility of certain ratios of frothers and collectors, e.g., oleate and long-chain sulphates, pine oil and soaps. Monolayer Penetration. Properties of insoluble films produced by molecules of surface active agents orientated at the air/liquid interface are conveniently studied by the Langmuir trough technique, described fully by Adam.' Using the trough technique Schulman and Hughes" and Schulman et al.10a. b, c, d,e established the existence of molecular interactions occur- ring between certain types of surface active agents. Their experiments revealed the phenomenon of penetration of an insoluble monolayer (e.g., a film of a long-chain alcohol) by a soluble agent (e.g., sodium alkyl sulphate) injected into the substrate (water or salt solution). The degree of molecular interaction taking place on penetration is determined by changes in the surface pressure of the resulting film, changes of its surface potential and its mechanical properties (viscosity and rigidity). When the interaction takes place between both polar groups and both hydrophobic groups of the two participating amphipathic molecules a molecular complex is formed. Complexes formed on penetration of the monolayer at interfaces are not necessarily true chemical compounds: they are labile in solution, the activity and reactivity of individual components are greatly different from those of the molecularly associated complex, and on crystallization they usually separate out into components. However, when formed in the orientated state at interfaces they are found to be very stable, although some mixed films spread as monolayers of stoichiometric complexes can show further penetration by subsequent additions of the soluble component injected into the substrate.'" The degree of association between two or more types of surface active agents is very sensitive even to small changes in electric (dipole) moment of the polar groups of the amphipathic molecules as influenced by magnitude and position of neighboring ions or dipoles, their size, concentration, and stereochemistry. In addition, the molecular association is greatly influenced by concentration and type of inorganic salts in the substrate, by its pH, and by temperature. The nonpolar groups of interacting molecules greatly affect the stability of molecular complexes. Progressive shortening of the aliphatic chain of one of the reacting molecules weakens (at an increasing rate) its tendency to form stable complexes. Similarly, introduction of a double bond of cis-form into one of the reacting chains, which changes the straight hydrocarbon chain into a kinked one, or introduction of a branched chain, reduces the stability of the associated complex. Monolayer Adsorption. Using the trough technique and injecting metal ions into the substrate (water or salt solution) underlying insoluble films of fatty acids, alkyl amines, and sulphates, Wolsten-holme and Schulman11a,b,e. ' and Thomas and Schulman" have established conditions, namely, pH, concentration. and steric factors, under which molecular interactions take place between the polar groups of the surface active agents and the metal ions. These interactions are marked by great changes in the solubility and mechanical properties of the monolayer of the agent; no surface pressure increases are observed as in monolayer penetration experiments. The results of these adsorption studies, correlated with flotation experiments, indicated that in the case of fatty acids and alkyl sulphates their adsorption onto minerals of base-metals takes place by a similar

Jan 1, 1955

By Katherine Mather

This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. Results of the properties of these rocks on their performance as concrete aggregates are discussed.

Jan 10, 1953