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By F. Keller, R. H. Brown

Because of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1, 2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. Not only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of A17s-T, 17s-T and 24s-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in 24s alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential difference between the core and coating may be less than 0.16 volt, depending uponIthe thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24s-T, two are generally used; namely, the metallo-graphic and the solution potential methods.3 Metallographic Methods Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24s-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. Consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By G. G. Brown

Enthalpy-entropy diagrams are presented for natural gases of 0.6, 0.7, 0.8, 0.9, and 1.0 gravity over the pressure range of 5 to 10,000 Ib. per sq. in. and temperature range of 32º to 700°F. The charts indicate directly the work requirement and temperature rise for adiabatic compression or temperature change for free emansion of natural eases. Computation and Uses of Charts The Mollier diagram (Fig. 4), in which the enthalpy (heat content) is plotted against the entropy with lines of constant temperature, pressure,, and in some cases volume, has been found most convenient when dealing with the compression, expansion, and flow of fluids. In dealing with the flow of fluids, the sum of the increase in the enthalpy, AH, plus the increase in kinetic energy, AM —, plus the increase in potential energy, ?MZ, representing the total increase in energy of the fluid in flow, is equal to the sum of the heat q, and work added, —w, to the fluid while flowing between the entrance and exit of the flow system. AH + AM— + ?MZ = q-w [1] In cases where there is no significant change in potential energy or in kinetic energy (velocity), it follows that the increase in enthalpy is equal to the total energy supplied to the fluid. Under such conditions' the changes in the property of the fluid as it flows through a throttling valve, choke, or any other similar arrangement, may be read directly from the enthalpy-entropy diagram by following a horizolltal line between the known pressures' When compressing Or expanding a gas by means of a Or or engine in which no heat is added to or subtracted from the gas, but only work done, the changes in the properties of the gas may be determined along a vertical line of constant entropy between the entering and exit pressures. The power required for the compression of the gas may be readily determined by converting the increase in enthalpy into the desired units. The enthalpy-entropy diagram for natural gases is to the gas engineer what the steam diagram is to the steam-power engineer. For this reason it would be extremely convenient if a reasonably satisfactory enthalpy-entropy diagram could be prepared as a function of the gravity of the gas. A careful study of the known properties of natural gas indicate that this is possible. The effect of temperature upon the enthalpy at constant pressure is expressed as the "heat capacity" or "specific heat" of the gas. The best available data for natural and petroleum refinery gases indicates the relationship shown in Fig. I. From this it is clear that the specific heat of natural gases is a function only of the gas gravity and the temperature at atmospheric pressure. The effect of pressure on the enthalpy of natural gases is dependent upon the pressure-volume-temperature relationships,

Jan 1, 1945

THE opening session was held on Tuesday evening, February 17th, in the house of the American Society of Civil Engineers. The President of the Institute, Mr. E. B. Coxe, after a few introductory remarks, congratulating the members on the general prosperity in all the branches of the professions and manufactures represented by the Institute, called on Mr. E. F. Loiseau, of Philadelphia, for the first paper, On the Successful Manufacture of Compressed Fuel at Port Richmond, Philadelphia. Professor Prime called attention to the fact that the work of the United States Testing Board had been left unfinished at a point when valuable results had just been reached, and offered the following resolutions: WHEREAS, The American Institute of Mining Engineers has seen with regret that the work of the United States Testing Board has been suspended through the lack of an appropriation by Congress, which appropriation dues not seem likely to be renewed, and WHEREAS, It seems most important to the vital interests of our iron and steel manufactures that the experiments commenced by the United States Testing Board should be carried to successful completion ; Resolved, That a committee of three be appointed, to act with a like, committee to he appointed by the American Society of Civil Engineers, to carry out to completion the work commenced by the United States Testing Board. Resolved, That the American Society of Civil Engineers be requested to cooperate with this society by the appointment of a like committee. Resolved, That the committee have authority to request, in the name of the American Institute of Mining Engineers, contributions to a fund to be devoted to the completion of the experiments aforesaid. Resolved, That the Council of this Institute be authorized, whenever requested by the committee so appointed, to petition Congress for the free use of the testing machine at the United States Arsenal at Watertown. Resolved, That a committee be appointed by the President, to select the afore-said committee of experts. Resolved, That the President of the Institute have authority to fill any vacancies which may occur in the committee. The resolutions were unanimously adopted, and President Coxe appointed the following committee in accordance with the resolutions : Messrs. A. L. Holley, James Park, Jr., and J. F. Holloway. The President also appointed Messrs. Heinrich, Mickley, and Spils-

Jan 1, 1880

By E. A. Slover

THE usual reverberatory system of smelting cop--1- per concentrate or calcine has for its component parts a furnace and one or two waste heat boilers. These parts are operated on a basis of compromise, since the furnace can send gas to the boilers at too high a temperature and the boilers by plugging, due to dust or slag, can place a definite limit on the amount of fuel the furnace can burn. Over the years the copper concentrate smelting furnace has had few advances in design. The simple rules of design such as the flame should wipe the bath and the speed of the gases should be reasonably low for dust carrying purposes seem to cover the main features. In the construction of the individual furnaces some innovations are always being introduced. Among these are charging so that the work of smelting is a complete bath process, the use of suspended brick arches in place of sprung arches, the use of basic brick, not only in the crucible, but also in roof and sidewalls, the use of various means to feed the charge, the use of magnetite or other heavy material to construct the hearth, water cooling of bridgewall and slag skimming bay, the smelting of raw charge instead of calcine, the use of preheated air, and possibly the use of oxygen-enriched air for combustion. But the general outlines of the furnaces have not changed much except as to size. Furnaces at Hurley As shown on Fig. 1, the furnace at Hurley is 126 ft long between the longitudinal buckstays and 32 ft wide at the skewback plates. The foundation is a concrete retaining wall with piers at intervals that go deeper into the earth. Purposely the wall at the burner end of the furnace is not backed-up as tightly as the other parts of the foundation so that movement due to expansion may take place here rather than into the boiler foundations. Within these foundation retaining walls of concrete, the earth has been removed to allow the placement of the crucible brick base inside of which a silica hearth is laid 4 ft 6 in. in depth. No expansion is left in the brick base and crucible where they are in contact with the hearth. The hearth itself is of quartzite crushed to 1 in. size with fines left in the product. An 8 in. layer is laid and tamped with paving tampers to about 6 in. in thickness. Then a layer of silica flour is spread and vibrated into the hearth. This operation is repeated until a depth of 4 ft 6 in. is occupied by the silica mass onion-skinned in layers of approximately 6 in. Before firing the entire hearth is covered with broken slag to a depth of 4 in. so that a seal may be formed on the hearth. The crucible is completely faced with magnesite chemically bonded brick while the outside, against the foundation, is made of silica brick. The side-walls are carried up with silica brick in which expansion joints are left at intervals. Above the crucible the sidewall is corbelled to form a shelf on which the charge may build up along the side-walls, see Fig. 2. The arch of the furnace is sprung 20 in. silica brick, with the longitudinal centerline horizontal the length of the furnace, and some 9 ft in the center above the bath. Both straight and wedge brick are used in the construction and a thin silica mortar is troweled for joints. After the arch under heat has assumed its permanent shape, a silica slurry is spread over the arch to fill any cracks that have formed, thus giving bearing surface to the brick and preventing dust from entering the body of the arch to act as a future fluxing agent. The uptake of the furnace slopes up to the boiler entrance where a brick pilaster divides the gas stream for the two boilers. Over this flared uptake is a suspended flat arch of firebrick. The pilaster and sidewalls are constructed of firebrick but the bottom of the uptake is lined with silica brick and fettled through holes in the roof with siliceous fettling. Close to the entrance of each boiler is a brick covered slot through which water-cooled dampers may be lowered in event of boiler trouble. These water-cooled dampers are hung permanently in position ready to be lowered when needed. Flexible hoses to follow the dampers as they are lowered are connected at all times and individual chain blocks are used to lower the dampers. A pump supplying water is started before the dampers enter the heat. Charging of the furnace along the sidewalls for some 80 ft from the bridgewall is accomplished by electric vibrating conveyors fed by belt from charge storage bins above the furnace. These conveyors

Jan 1, 1954

By M. J. Spendlove, H. W. St. Clair

The problem frequently arises, particularly in refining metals or smelting scrap metals, of separating metals in the metallie state. Many metals may be separated by taking advantage of their difference in vapor pressure. Such separations can be made at atmospheric pressure, but the separations are much more selective and can be carried out at considerably lower temperatures if the distillation is done at pressures of a few millimeters or less in an evacuated enclosure. Until recently, this has not been considered feasible as a metallurgical operation, but the recent improvemcnts that have been made in vacuum technology have broadened the applicability of vacuum processes and have prompted re-examination of low-pressurc distillation of metals as a practicable process. The distillation of zinc from lead is one separation that has already been reduced to practice.l This paper is the first of a series of studies being made on separation of nonferrous metals by distillation at low pressures. Although these experiments were confined to the separation of zinc from aluminum, the significance of the results is by no means confined to these two metals. The purpose has been to investigate a metallurgical technique rather than merely to devise a means of separating specific metals. The experimental work on distillation of zinc from zine-aluminum alloys at reduced pressure grew out of earlier work on distillation at atmospheric pressure.2 The earlier work indicated that it would not be practicable to decrease the zinc in the alloy much below 10 pct owing to the high temperature required. Therefore attention was turned to distillation ah low pressures, at which lower temperatures are required. After preliminary tests were made in a small, evacuated tube furnace, a larger furnace having a capacity of 100 to 150 Ib of metal per charge was constructed. Distillation tests were first made on pure zinc and then on aluminum-zinc alloys of various composition. Particular attention was given to the limit to which zinc could be reduced in the residual metal. Data were also taken on the rate of evaporation, and heat balances were made for both the crucible and the condenser. Distillation Furnace The vacuum-distillation unit is illustrated schematically in Fig 1. The major components are the induction furnace, the condenser, the vacuum system, and the power-conversion unit. Power is supplied to the induction furnace from a 50-kw 3000-cycle motor-driven alternator. The pressure in the furnace is reduced by a vacuum pump having a nominal pumping speed of 10 liters per sec. When in operation, the metal vapors travel upward from the furnace to the water-cooled condenser where they are collected in amounts of 50 to 100 lb. The condenser is removed with aid of an electric hoist. When the system is under vacuum, the condenser is made self-sealing by a rubber gasket between the smooth-faced, water-cooled flanges at the top of the furnace and the bottom of the condenser. The pressure of the atmosphere is more than sufficient to insure sealing. At the conclusion of an experiment, the residual metal can be removed from the furnace by removing the condenser and tilting the furnace with the electric hoist. The metal was cast into the molds carried on a mold truck. A photograph of the furnace and auxiliary equipment is shown in Fig 2. The details of the vacuum furnace are illustrated in Fig 3. The furnace proper is made vacuum-tight with rubber gaskets placed at each end of a fused quartz cylinder. A clamping plate at the bottom and a ring at the top are made to squeeze the rubber between the metal and the end of the quartz tube. A large graphite crucible placed inside the quartz cylinder is thermally insulated and physically supported by refractory insulating bricks. A thermocouple in a quartz protection tube is located at the bottom of the crucible: the leads pass through a rubber seal in the bottom plate. The supporting structure for the furnace is an angle iron frame with transite board sides. The condenser is made in the form of a water jacketed cylinder with an opening to the vacuum line at the top. The bottom has a projecting skirt inside the machined flange to provide additional cooling for the rubber gasket. Condenser sleeves are made in the form of two semicylindrical pieces of sheet metal that fit snugly inside the cooling jacket. The split sleeve facilitates removal of the condensate. Measurement of Temperatare and Pressure The metal temperature was measured by a platinum-platinilm rhodium thermocouple inserted in a well extending up into the bottom of the graphite crucible. During rapid evaporation there is a wide difference in temperature between the surface and the main body of metal in the crucible because of the large amount of heat that must be conducted to the surface to supply the heat of evaporation. The heat of

Jan 1, 1950

By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.'- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin' has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled' that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By B. E. Lindsly

The withdrawal of gas and/or oil in appreciable quantity from a natural oil reservoir causes the pressure within the reservoir to diminish, and if the oil is completely saturated with gas, this dissolved gas begins to evolve from solution. The liberation of gas from solution in oil causes the oil to change in several ways, the principal changes being: (1) reduction in volume or "shrinkage"; (2) increase in specific gravity (decrease in degrees A.P.I.); (3) decrease of energy in the oil; (4) increased viscosity; (5) increased surface tension. As the writer's investigations have been concerned more with the first three items than with changes in viscosity and surface tension the following discussion relates particularly to the volumetric shrinkage of the oil, to the increased specific gravity, and to the decreased energy in the oil, each caused by the liberalion of dissolved gas. One of the most surprising facts that have developed in the study of high-pressure well-head and "bottom-hole" samples is the great reduction in volume that occurs in some oils when the naturally dissolved gas is liberated. High-pressure samples taken from well heads in the Oklahoma City, Kettleman Hills and Ventura, Calif., fields decreased in volume from 11.2 to 40.5 per cent when the dissolved gas was liberated in reducing the pressure on the sample to atmospheric. The amount of shrinkage an oil undergoes when gas is liberated depends upon the quantity of gas liberated and also upon its composition. A given volume of the heavier gases, propane and butane for example, will occupy more space in the oil than an equal volume of methane. The reason for this probably is that the molecules of the heavier gases are larger than those of the lighter gases. When gases are not in solution, and particularly when they are at low pressures, the distance between the gas molecules is so much greater than the dimensions of the molecules themselves that the mere size of the molecules has little effect upon the space occupied by the gas, Avogadro's hypothesis, which in effect states that all gases under the same conditions have the same number of molecules per unit volume, relates to this phenomenon. The fact that the heavier gases occupy more space than the lighter gases in the oil, and

Jan 1, 1934

By A. F. Taggart, Nathaniel Arbiter

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles' of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By R. V. Norris, E. W. Parker

Edward W. Parker,* Philadelphia, Pa.—At the New York meeting of the Institute a year ago, Mr. R. V. Norris presented a paper on anthracite mining costs, in which he gave the results of an intensive study of this subject by the Engineers' Committee of the United States Fuel Administration. Within the last 30 days, the Federal Trade Commission has issued an official report on the same subject, which covers a longer period of time and comprises statistics of realization values and margins that were pot comprehended in the paper by Mr. Norris. As, however, the data utilized by Mr. Norris formed also a part of the basis for the report of the Federal Trade Commission, a brief digest of the latter may not be out of place at this meeting. The report of the Federal Trade Commission covers primarily the two calendar years 1917 and 1918, divided into five periods which furnish opportunity for the study of how the influence of certain definite factors affected either the cost of production or the price, or both, during the 24 months. The first period, January to April, 1917, which may be considered the basic period, comprised the 4 months in 1917 during which the wage agreement of May, 1916, without modification, was in effect. During this period, the labor cost on fresh-mined coal is placed by the Commission's report at $1.79 per gross ton, the total cost at $2.66, the average realization at $3.29, and the "margin" (sales realization over total f.o.b. mine cost) at $0.63. The second period covers the four months from May 1 to August 31, during which time the first of the supplemental wage agreements (supplemental to the agreement of 1916) was in effect. It was also the period during which the summer discounts were in effect and when prices were practically fixed by a voluntary agreement between the operators and the Federal Trade Commission. It was, further, the period in which the 75 cents differential on prepared sizes permitted to the individual operators by the Federal Trade Commission began; at that time, also, on account of war conditions an unusually large quantity of steam sizes were marketed at exceptionally good prices. On account of the two latter conditions, not explained in the Commission's report, the "margin"1 on operating

Jan 1, 1920

By Nathaniel Arbiter, A. F. Taggart

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles' of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By J. W. Paul, J. N. Geyer

The measures overlying some coal beds are under stress as the result of geological movements after the measures have been deposited. The removal of the coal in the process of mining induces additional stress in the roof measures. Certain types of deposits have sufficient inherent strength to be self-supporting over definite width of excavations and the stress is adjusted without appreciable movement of the material, to the extent that no part of the material will become detached and fall. The uplifting of the measures in geological time often results in the establishing of cleat planes or planes of weakness in the measures overlying the coal, and these planes generally have a uniform direction. Measures that have not been subject to uplifts are less liable to have noncompensable stresses, although any method of underground mining results in the creation of stress in the roof measures over the excavations and over the coal pillars. The immediate roof measures extending upwards of 10 to 15 ft. above the coal give the greatest concern in maintaining the roof in the advance work in the solid coal. Immediate measures which are inherently weak often may be scaled and supported for indefinite periods by a system of timbering. As an excavation is made, the pillars adjoining must take on the weight previously supported by the coal removed. The roof over the excavations takes on the function of a beam and if too weak to be self-supporting it will fail either through shearing or bending, and the roof cavity may enlarge until a self-supporting arch is formed. As support is removed by taking the coal away, there is a tendency for the roof members to move toward the excavation in an effort to compensate the stress; particularly is this true where there is an overlying bed of clay, which may act as a lubricant on which adjoining members may slide. Unstabilized stresses, plus the force of gravity, plus the inherent strength of the material, govern the tendency of mine roof to fall when not supported by timber. In general, most mine roof depresses when the coal is removed. This depression may be in the nature of a sag as the result of bending, or the edges of the pillar may break away or the floor may come up or heave.

Jan 1, 1934

By J. B. Tyrell

A SHORT time ago I paid a visit to the alluvial gold fields on the tributaries of the Chaudière River in Beauce County, Quebec, in company with A. 0. Dufresne, late manager of the Champs d'Or Rigaud-Veaudreuil, and now Assistant to the Superintendent of Mines of the Province of Quebec. As the conditions under which the gold occurs in this district are not very generally known, and present some interesting features, a brief description of these conditions, and a consideration of the causes which gave rise to them, may be of interest to other mining engineers. During the latter half of last century the country was visited by many mining engineers and geologists, and many references to it may be found in the reports of the Geological Survey of Canada between 1848 and 1911. The most important of these are by J. A. Dresser and J. Keele and the late Robert Chalmers. The Department of Colonization and Mines of the Province of Quebec also published a report with map on the district by J. Obalski. From the earliest times the valley of the Chaudière River formed one of the main avenues of approach to the St. Lawrence in the vicinity of Quebec from the country to the south as far as the seaboard of the States of Maine and Massachusetts. The Indians had a well-known trail along the banks of the stream, and armed troops and foraging parties constantly moved backward and forward along it between Quebec and New England in those insecure times before the ceding of Canada to Great Britain. Even yet the natural advantages of this old military route are recognized, and the government of the -Province of Quebec has now under construction along it a magnificent highway from Quebec to the International Boundary Line, which is to form part of a through highway from that city to Boston; The land along the valley is naturally well suited for agriculture, and about the end of the eighteenth and the beginning of the nineteenth centuries farmers began to go back from the St. Lawrence, and to occupy the higher lands along the upper portions of the Chaudière Valley. This settlement has gone on until now the country is peopled with a prosperous agricultural population.

Jan 3, 1915

By J. B. Tyrrell

A short time ago I paid a visit to the alluvial gold fields on the tributaries of the Chaudiere River in Beauce County, Quebec, in company with A. 0. Dufresne, late manager of the Champs d'or Rigaud-Veaudreuil, and now assistant to the Superintendent of Mines of the Province of Quebec. As the conditions under which the gold occurs in this district are not very generally known, and present some interesting features, a brief description of these conditions, and a consideration of the causes which gave rise to them, may be of interest to other mining engineers. During the latter half of last century the country was visited by many mining engineers and geologists, and many references to it may be found in the reports of the Geological Survey of Canada between 1848 and 1911. The most important of these are by J. A. Dresser and J. Keele and the late Robert Chalmers. The Department of Colonization and Mines of the Province of Quebec also published a report with map on the district by J. Obalski. From the earliest times the valley of the Chaudiere River formed one of the main avenues of approach to the St. Lawrence in the vicinity of Quebec from the country to the south as far as the seaboard of the States of Maine and Massachusetts. The Indians had a well-known trail along the banks of the stream, and armed troops and foraging parties constantly moved backward and forward along it between Quebec and New England in those insecure times before the ceding of Canada to Great Britain. Even yet the natural advantages of this old military route are recognized, and the government of the Province of Quebec has now under construction along it a magnificent highway from Quebec to the International Boundary Line, which is to form part of a through highway from that city to Boston. The land along the valley is naturally well suited for agriculture, and about the end of the eighteenth and the beginning of the nineteenth centuries farmers began to go back from the St. Lawrence, and to occupy the higher lands along the upper portions of the Chaudiere Valley. This settlement has gone on until now the country is peopled with a prosperous agricultural population.

Jan 1, 1915

By H. J. Stehli

The first sintering of zinc ores was done at the Bartlesville plant of the National Zinc Co., under the auspices of the late Otto Rissman. Mr. Rissman, who had had a long experience in the treatment of zinc ores, well realized all the difficulties of satisfactorily roasting zinc concentrates, which were becoming finer and dustier as each year went by—thus increasing the difficulties of roasting them in the existing forms of roasters, which were furnaces of the Ropp, Hegeler or similar types. Mr. Rissman's idea of the advantages of sinter was expressed in this way: in a zinc ore dead-roasted in a mechanical furnace there are many particles that are just like an egg; that is, they have a hard and impervious film of fused material on the outside, and in the retorting this completely cuts off access of the reducing gases to the center of the egg until a temperature has been reached at which this shell of the egg can be broken down through fusion. A particle of sintered zinc sulphide, on the contrary, is exactly like a piece of sponge. The moment the retort reaches the temperature at which the reactions can take place, they begin, because the reducing gases have ready access to the interior of the particles by means of the pores of the '" sponge." His faith in the advantages of sinter was amply borne out by the results obtained at the pioneer sintering plant for zinc ores installed by the National Zinc Company. Early Method of Sintering The method of procedure at Bartlesville was to roast the zinc concentrates down to somewhere in the neighborhood of 8 per cent residual sulphide sulphur; to cool these, then to wet them down to the proper moisture and mix them in the mixer of the sintering plant; then to sinter them by means of the heat available from the residual sulphides. The sulphur contents of the roast varied considerably, of course, as it was difficult with the furnaces in use to control the roasting exactly at any point short of dead roast. Hence at times the concentrates were roasted a little too low to sinter readily, and at such times the lack of sulphur was made up by the addition of raw concentrates to the sintering-machine charge in suitable amount.

Jan 1, 1937

By G. C. Stone

The method of making oxide of zinc direct from the ore was invented and developed at the works of The New Jersey Zinc Co. at Newark in the middle of the last century. The process was invented by Burrows, who had not the ability, financial or technical, to work out the details necessary to make it of commercial value. This was done by Col. Wetherill, whose name is commonly attached to this process. The grate bars used are also frequently called Wetherill grates, which is a misnomer because they were in common use for boiler firing at the time, and he never claimed their invention. The invention of the process was due to the efforts of The New Jersey Zinc Co. to find a profitable means of working the ores from Franklin and Sterling Hill, N. J. These are a mixture of franklinite, willemite, and zincite, containing about 20 per cent. of zinc. The first attempts were to make spelter, which were not successful, owing to the low grade of the ore and the fusibility of the residue. Failing in this, the next attempt was to make oxide in large muffles and reverberatory furnaces. This succeeded, although the cost of operation was high, the recovery low, and the quality of the product uncertain. In 1855, the new process was patented and has been in successful operation ever since. Essentially, the process is to spread a mixture of coal and ore on a body of burning coal on a perforated grate, and blow an excess of air through the grate. The zinc is reduced in contact with the coal, volatilized and burned by the excess of air in the upper part of the furnace and in the flues. It is then carried to the bag rooms by the excess air and products of combustion which are foreed through the flues by fans. In its main features, the process is the same today as at the time of its invention, but the details have been so modified that it would hardly be recognized by its originators. OrEs The process is applicable to all the oxidized ores of zinc and to roasted sulphides, provided the gangue is not so fusible as to leave a residue that is impervious to the blast. In many cases the ores contain impurities that make it impossible to produce an oxide of a good enough color to be

Jan 1, 1918

By H. Landssberg

Subsidence caused by mining operations has been a matter of interest for the mining engineer for just 111 years, since the Belgian committee for study of subsidence in the city of Liege submitted its first report in 1825. This interest is fairly expressed in the enormous amount of literature that has since appeared on this subject. A bibliography, probably far from being complete, which preceded this study as a preliminary survey, comprises more than 800 titles. In spite of this fact the problem remains today as acute as it has ever been. The questions of as good a recovery as possible of the national resources, the safety of the operations, and the protection of private and public property are the important angles from which to look at the problem. The Problem To systematize an investigation regarding the effects of mine excavations two different aspects have to be dealt with: (1) the subsidence of the immediate roof above the workings, affecting the safety of the workers and the progress and efficiency of the operations; (2) the subsidence of the surface, which is also, from the point of time, the second event. The immense importance of surface subsidence as regards the impairment of surface structures of every kind in a mining area is self-evident. Both effects result from reactions of the strata overlying the excavations and they depend mainly on the extent of the excavations and the structure and geological condition of the strata. It has been stressed repeatedly, in this country principally by G. S. Ricel,† that for the understanding of the phenomenon of subsidence accurate surveys are the most urgent necessity. In the past, however, at least in the normal course of mining operations, these surveys have been very crude. The control of the roof in the mine is left to the observation of the behavior of the timber, warning cracks and sounds in roof and walls and to the general judgment and experience of the worker and his supervisors. In any given case this may or may not be sufficient to prevent fatalities but certainly it does not give any accurate information as to what is happening in roof and strata. On the surface, principally in endangered areas, surveys have been conducted more frequently, but also in this case usually weeks or even

Jan 1, 1936

By H. Landssberg

Subsidence caused by mining operations has been a matter of interest for the mining engineer for just 111 years, since the Belgian committee for study of subsidence in the city of Liege submitted its first report in 1825. This interest is fairly expressed in the enormous amount of literature that has since appeared on this subject. A bibliography, probably far from being complete, which preceded this study as a preliminary survey, comprises more than 800 titles. In spite of this fact the problem remains today as acute as it has ever been. The questions of as good a recovery as possible of the national resources, the safety of the operations, and the protection of private and public property are the important angles from which to look at the problem. The Problem To systematize an investigation regarding the effects of mine excavations two different aspects have to be dealt with: (1) the subsidence of the immediate roof above the workings, affecting the safety of the workers and the progress and efficiency of the operations; (2) the subsidence of the surface, which is also, from the point of time, the second event. The immense importance of surface subsidence as regards the impairment of surface structures of every kind in a mining area is self-evident. Both effects result from reactions of the strata overlying the excavations and they depend mainly on the extent of the excavations and the structure and geological condition of the strata. It has been stressed repeatedly, in this country principally by G. S. Ricel,† that for the understanding of the phenomenon of subsidence accurate surveys are the most urgent necessity. In the past, however, at least in the normal course of mining operations, these surveys have been very crude. The control of the roof in the mine is left to the observation of the behavior of the timber, warning cracks and sounds in roof and walls and to the general judgment and experience of the worker and his supervisors. In any given case this may or may not be sufficient to prevent fatalities but certainly it does not give any accurate information as to what is happening in roof and strata. On the surface, principally in endangered areas, surveys have been conducted more frequently, but also in this case usually weeks or even

Jan 1, 1936

By V. E. Christensen

AT most smelting plants, forced draft, induced by high stacks or fans, is used to carry the gases away from the furnaces, roasters, or sintering plants. Gases moving under forced draft carry varying amounts of solids in the form of dust and fume. Where the weight of the solids is material, and the metal content high, it is usually profitable to treat the gases to recover these solids. Baghouses, Cottrell treaters, and settling chambers are the common forms of plants used to recover solids from gases. To check on the efficiency of these plants it is necessary to know the volume of gas leaving the plant and the amount of solids carried by the gas. As the volume of gas is equal to the product of the velocity of that gas and the cross-sectional area of the flue, the determination of the volume includes the measurement of the area of the cross section and the determination of the velocity. The velocity is generally measured by means of the Pitot tube and Ellison differential pressure gage, although low velocities are best determined by means of an anemometer. The dust concentration is determined by passing a measured volume of sample through a filter and weighing the dust caught. From this the dust concentration per unit of volume may be calculated. It is necessary to assume that the gas is homogeneous or that each cubic foot of the gas contains the same weight of dust as every other cubic foot. Having the volume of gas passing through a flue per unit of time, and the dust concentration of the gas per unit of volume, the amount of solids may easily be calculated.

Jan 1, 1935

By Irwin R. Higgins

CONTENTS A. Introduction B. System Description C. Uranium Pilot Plant Programs D. Summary INTRODUCTION The Chem-Seps Continuous Countercurrent Ion Exchange (CCIX) contactor was first conceived of in 1951 at the Oak Ridge National Laboratory. In the 27 years that have passed, there has been a steady stream of pilot plant process development studies on a variety of processes far too numerous to mention. These have been in the area of water and waste treatment, chemical processing, ore leach treatment, and many others. Many successful production systems have been installed and operated in a variety of applications. A few of these are described herein together with a description of the system and its operational characteristics. SYSTEM DESCRIPTION Chem-Seps Continuous Countercurrent Ion Exchange* is a single loop in which various sections are separated by valves to isolate the sections performing different functions simultaneously. (Refer to Figure 1). To explain the working of a typical unit, let us use a simple configuration used in water softening or demineralization. The resin is moved in small increments by the hydraulic ram action. All solution flows are countercurrent to the flow of resin. The contaminants are removed in the process cycle and the resin is moved in the pulse cycle. A controller in the effluent stream from the treatment section senses the proper limit permissible in the effluent. In the process cycle, the influent enters through a set of distributors, moves downward and leaves through a set of collectors. Simultaneously the regenerant enters through valve RE and leaves through valve WA. The rinse enters through valve RI and its duration is controlled by an interface controller. In the process cycle, valves B, C, and D are closed, isolating all the sections. The duration of the process cycle is 4-10 minutes depending on the contaminants to be removed and is controlled either by a timer if the contaminants are fixed, or a controller in the effluent stream, if the contaminants fluctuate at short intervals. Valve A is open and resin is dropped to the pulse section simultaneously with the removal of contaminants in the treatment section, regeneration of loaded resin in the strip section, and rinsing of regenerated resin in the rinse section. As the resin drops through the valve A, it is backwashed to remove the suspended solids or resin fines. Removal of these fine particles is important to avoid the unnecessary pressure drop in the bed and plugging of the distributors. At the end of process cycle, all flows going into the unit and out of unit are automatically shut off. The valve A closes and valves B, C, and D open in proper sequence. A slug of water enters through valve PU, a predetermined incremental volume of resin moves into the regeneration section, an equal volume of regenerated and rinsed resin enters the bottom of the treatment section, and an equal volume of the loaded resin leaves the top of the treatment section and goes into the resin reservoir section. (The resin movement is plug flow with the Reynold's number being in the laminar region of the curve, and no fluidization occurs during the pulse cycle.) The total time required for proper sequencing of valves and the movement of resin is 20-30 seconds. At the end of this period, the valves B, C, and D close and valve A opens. The solution valves open and normal steady state operation begins. All valves are interlocked and properly sequenced. The resin movement is precisely controlled by sonic devices. Special Features of Chem-Seps CIIX "Downflow"*: The raw feed in the treatment section moves downward and the resin moves upward in the treatment section. The "downflow" of feed overcomes the handicap encountered in "upflow" systems. The "upflow" of feed requires a certain minimum flux during process cycle to lift the bed and keep it

Jan 1, 1979

By R. L. Schmidt, J. D. Verhoeven

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.

Jan 1, 1968