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By H. Sato, I. Matsuoka, T. Kawai, S. Hasebe

In a limestone mine, a large amount of slime is washed off in order to remove impurities such as clay minerals. A fine sized calcite is, consequently, wasted and freight for carring the slime to reclaim land is expensive. The separation of calcite from the slime has been investigated by the flotation process, using sodium oleate as a collector. A satisfactory flotation of calcite from the slime requires great amounts of sodium oleate, because sodium oleate is consumed by clay minerals. But, the amounts of sodium oleate required are reduced to half by adding suitable amounts of sodium silicate. After rougher and cleaner flotation, the concentrate containing more than 97% calcite is obtained with 70% recovery; thereby the amount of slime to be reclaimed is reduced to 40%.

Jan 1, 1976

By P. Raffinot, M. Rey, V. Formanek, G. Sitia

Six years of laboratory study, followed by three years of mill operation treating more than 10,000 tons of ore, have established the flotation of oxidized zinc ores with fatty amines as an efficient process. Recently the method has been applied with success to partially oxidized sulphide ores. In this paper the authors give an account of their research and the milling results obtained in Sardinia since 1951. CONCENTRATION of oxidized copper and lead ores by flotation has been practiced for 30 years, but flotation of oxidized zinc ores has remained unsolved until a few years ago. This problem is, however, of great importance in mining districts where large tonnages of oxidized zinc ores exist in underground mines or in dumps. Some sulphide ores also possess a degree of oxidation high enough to justify recovery of oxide zinc minerals. Various attempts have been made to float the zinc carbonate, smithsonite. It is well known' that smithsonite can be collected with fatty acids, but as the predominant gangue constituents, limestone and dolomite. are floatable with the same reagents, fatty acids are difficult to use. Gaudin has shown,' on mixture of pure minerals, that smithsonite can be floated with higher xanthates, or better, with higher mercaptans. Another procedure, briefly mentioned by Davis," consists in sulphidizing the ore, activating the zinc carbonate with copper sulphate, and floating with ordinary xanthates. This process was attempted in the writers' laboratory in 1946, but results were erratic. It has since been taken up by Italian engineers and is in operation on certain types of ores. Two other research projects should be mentioned. In 1942 Erlenmeyer and others' floated synthetic mixtures of smithsonite and gangue minerals with hydroxyquinoline, an analytical reagent for zinc. On the other hand, Bunge, Fine, and Legsdin published in 19465 Some interesting results obtained on Missouri oxidized zinc ores. With sodium oleate as a collector and a combination of sodium hydroxide, sodium silicate, and citric acid as a limestone depressor, they secured, after four cleaning operations, a good grade of concentrate. With many ores this reagent combination lacks adequate selectivity. In 1939 M. Rey initiated a program of research on this important problem. Work was pursued first at the School of Mines in Liége, Belgium"' and later in Paris in the laboratories of Société Miniére et Mbtallurgique de Penarroya and Société Minerais et Métaux. Reagents used in the beginning were higher xanthates and mercaptans, later fatty amines. Sulphidization with sodium sulphide was found necessary. These conditions make possible the flotation of zinc carbonate and zinc silicate. Two milling plants were put in operation in Sardinia in 1950 and several others are now contemplated." ' It should be mentioned that unknown to the present writers McKenna, Lessels, and Peterson were

Jan 1, 1955

By AIME AIME

EVER since Henry Bessemer, nearly 100 years ago, developed the steelmaking process that bears his name, occasional variation has been noted in the quality of steel made in the acid converter, owing largely to the difficulty of stopping the ? refining-which takes only ten to twelve minutes -at precisely the right moment. Principally as the result of this, the amount of Bessemer steel made in the United States gradually declined over the years until it is now about 7 per cent of the total.

Jan 1, 1943

By V. C. Wansbrough

A LUCID, thorough and powerful review of the impact of your tax laws on mining operations has already been presented by Granville S. Borden*. He has brought into focus and relief the pressure-points at which the shoe pinches most, has suggested some remedial measures, and enunciated much sound doctrine about the interrelationship and interplay of taxation policy and mining activity. Under the heading "What Every Lawmaker Should Know", he laid down the fundamental proposition that "the magnitude of our mineral resources varies inversely with the magnitude of the taxes levied upon them." With this, as with his other major premises, all mining men must be in hearty concurrence. There can be no doubt that a flourishing and expansive future for the mining industry in this country, in Canada, or anywhere else will depend on the thoroughness with .which these fundamental propositions are grasped by legislators, by national policy-makers and by public opinion at large.

Jan 1, 1950

Louis D. MILLS, San Francisco, Cal. (written discussion *).-The principle involved in the Crowe vacuum precipitation process is so elementary and the apparatus required is so simple, that the whole subject affords scant material for a technical discussion. As. one prominent Colorado metallurgist recently remarked when asked to contribute to this paper: "The Crowe process is the biggest step forward since the early clays of the cyanide process, but there is nothing to write about; just put it in your mill and try it." The writer confesses to a similar feeling, but having been closely identified with the process since its inception in 1916, he is perhaps in a position to at least comment on the theory involved and to record some of the results that have been achieved in actual practise. In practising the Crowe process, the solutions to be precipitated are first vacuumized in a suitable dispersion tower; that is, thin films of the liquid are subject to the action of a vacuum within a receiver. Sub-

Jan 1, 1919

By Howard N. Hall

The compressibility of reservoir rock is a factor which is generally neglected in reservoir engineering calculations. This is due in part to the fact that there is little published information on rock compressibility values for limestones and sandstones. Omission of rock compressibility is undoubtedly justified in calculations for saturated reservoirs; however, in under-saturated reservoirs,* expansion of the rock accompanying decline in the reservoir pressure may be of such magnitude as to affect materially the prediction of reservoir performance. The effect of rock compressibility will be of most importance in: (1) calculation of oil in place by pressure decline data in undersaturated volumetric reservoirs when the limits of the field are unknown or indefinite, and (2) studies of natural water drive performance. To estimate its importance in such cases, a series of laboratory tests were made to obtain usable values for reservoir rock compressibility. The total, or effective, compressibility of any reservoir rock is a result of two separate factors, namely, expansion of the individual rock grains, as the surrounding fluid pressure de-

Jan 1, 1953

By C. M. Schwerin

It is often necessary to calculate the size of a hoisting-plant required to raise a given quantity of material, either as a preliminary to the detail design of the machinery, or to decide whether machinery on hand or offered by a manufacturer is adapted to the work to be done. The first element of the problem to be determined is the load to be raised. In a mine that is already developed, this is limited by the size of car that can be hoisted out of the mine and that will pass through the underground gangways. If these place no limits on the design, the size of the load will depend on the output desired per day, and on the number of hoists that call be made per day. The latter are fixed by the time required per hoist and the number of hours available for hoisting, after deducting from the working-day the time required for raising and lowering men, sending down supplies, and for the many small delays in handling cars. It must also be decided whether the hoisting is to be done in one shift or in all of them.

Jan 1, 1903

By J. H. Swisher

HIGH-temperature anneals in wet hydrogen are widely used in research as a technique for decarburiz-ing Fe-C alloys. This technique is also used commercially in processing low-carbon steels for magnetic applications. The results of some calculations to be presented show that for temperatures up to 1100°C there is a critical temperature for maximizing the decarburization rate of alloys containing about 0.1 pct C. The low-temperature portion of the iron side of the Fe-C phase diagram1 is reproduced in Fig. 1. Preliminary calculations show that the critical temperature is between 727" and 905°C. In this range, the alloy contains two phases during heat treatment, ferrite and austenite. Decarburization therefore occurs by a process termed "diffusion accompanied by a phase change".' For intermediate stages of decarburization, the carbon concentration profile in a flat plate is shown in Fig. 2. The carbon content increases linearly from zero at the surface to a value, cB , at the two-phase boundary. cB is known from the phase diagram, see Fig. 1. At the interface where x = 5, the carbon content increases to ci, the initial concentration in the alloy. smith3 has derived an equation which describes the rate of movement of the boundary. With a rearrange-

Jan 1, 1969

By B. Das, V. Hucka

In light of the present energy crisis, coal appears now as the only reliable source of energy. The production of coal is expected to regain a rising trend after the latest slump. Aside from the competitive price with natural gas and oil, the other retarder of coal production is its environmental pollution effect. Gasification of coal has been advanced as the partial solution to the energy-ecology crisis. All the Advantages In situ gasification of coal may be considered a further step in this direction. It carries all the advantages of normal coal gasification as a stable source of energy; it is clean to handle and nonpolluting of the environment. It partially and sometimes fully does away with mining, makes uneconomical low grade coal and lignites economical and places some formerly unworkable seams within the scope of modern technology. The seams posing problems for mining due to tectonic disturbances may be converted into gas in situ. Low grade coals, such as lignites, which otherwise would be left in nature as uneconomic wealth, may be exploited by underground or in situ gasification. Thus, in situ gasification is likely to increase the exploitable reserves of coal and may reduce the cost of production. An additional merit of this method is that coal substance never reaches the surface and there is no problem of cinder disposal.

Jan 8, 1973

Another excellent Swedish underground crushing plant is that at Crusher Station 51 of LKAB in Kiruna, Sweden. Bottom-dump rail cars pass over a dump scroll to discharge magnetite ore into a 288 cu yd (220 m3) pocket equipped with a Hewitt Robins E-13 vibrating grizzly feeder. The grizzly section is 59 in. (1500 mm) long and has bar spacings 3 in. (76 mm) wide. Any oversize boulders which will not pass the chute opening to the feeder are blasted. The primary breaker is a Morgardshammar overhead eccentric 55 in. by 71 in. (1400 by 1800 mm) jaw crusher powered by a 200 hp (149 kw) motor. An open side setting of 10. 8 to 11. 8 in (275 to 300 mm) accounts for the high capacity of this crushing unit (2760 stph or 2500 mtph). This figure compares favorably with the capacity of many gyratory crushers but is typical of the Swedish jaw crushing installations, which are often followed by three more stages of crushing or by autogenous grinding. Crushed ore from the jaw crusher is combined with the grizzly under- size in the crushed ore pocket and is fed by a second vibrating grizzly feeder to the secondary cone crusher. Both crushers are serviced by 50/5 ton overhead bridge cranes. During maintenance operations air -operated gates shut off the flow of ore from the dump and primary crushed ore pockets.

Jan 1, 1978

By B. G. Matson, M. A. Whitfield, G. R. Dysart

This paper describes the development of u computer program to calculate changes that occur in the length of tubular goods due to temperature and pressure changes during stimulation operations. Due to the numerous variables involved and the uncertainty of all static and dynamic conditions that could exist, it becomes a staggering task for individuals charged with completions to perform the necessary mathematical calculations. The computer program permits advance calculations for several sets of conditions. INTRODUCTION In the Delaware basin of West Texas alone, 50 wells were contracted or drilled to 15,000 ft or deeper in 1965. Deep well activity is continuing in this and other areas on an expanding scale. Many of these deep wells require extensive stimulation for successful commercial production, and during these operations, pressures and temperatures are encountered that have a pronounced effect on the length of tubular goods. This length change during a large-volume, high-pressure stimulation treatment utilizing fluids considerably cooler than bottom-hole temperature can be of such a magnitude that permanent damage to casing and tubing will result unless mechanical design, pressures and fluid temperatures are evaluated and controlled. These pressure and temperature effects can be calculated. However, the process lends itself well to computer solutions because of the mathematical nature of the problem and the calculating hours involved in arriving at an answer. The engineering-hour demand becomes more severe as tapered strings are involved. On initial treatments on a given well, surface pressure and injection rate conditions are unknown, and offset well conditions have not proven to be a reliable method for making predictions. For these reasons, it has become rather standard procedure for operators to compensate for these uncertainties by placing unnecessary pressure and fluid temperature restrictions on stimulation design. On a number of occasions treating fluids have been preheated to as much as 160F as a means of compensating for thermal contmction resulting from pumping cool fluids. The maintenance of packer seals has been treated by Lubinski, Althouse and Logan',' and the problem of therma1 effects on pipe has been explored by Ramey." These works were expanded and the results made applicable to everyday oilfield terminology before submitting them to computer programming. The pressure and temperature effects on tubing movement previously mentioned occur simultaneously as fluid moves through the pipe. The pressure changes, for purposes of explanation, are categorized here as to the various effects these pressures have on a tubing string. These divisions are (1) the piston-like results of forces acting on horizontal surfaces exposed to pressure, (2) swelling or ballooning of the tubing along its entire length due to the forces of pressure acting against the tubing walls, (3) the elongation of tubing due to frictional drag and (4) corkscrewing of the pipe due to internal pressure. Thermal changes are also of great importance, as their results may be more significant than any of the pressure effects. Steel is an excellent conductor of heat and the earth is a relatively poor conductor. It has been calculated that pipe temperatures at depths of more than 20,000 ft approach within as little as 25" the temperfature of the surface fluid after pumping for 2 hours, or a drop in temperature in some treatments of more than 220F. The equations presented in this paper were developed for computer programming and simplicity of input information; therefore, numerical constants such as Young's modulus for steel (28 X 10\ si), the coefficient of thermal expansion of steel (6.9 X 10."IF) and Poisson's ratio for steel (0.3) are included with unit conversion factors. The moment of inertia of tubing cross-sectional area with respect to its diameter was changed to a constant times (D' — d') where D is outer diameter and d is inner diameter. Units in the equations are length in feet, diameter in inches, density in pounds per gallon, pressure in psi, rate in barrels per minute and time in hours. PISTON-LIKE REACTIONS A change in tubing internal dimensions and the exposure of other horizontal surfaces to different pressures on the inside and outside of the tubing result in a reaction much like a piston under pressure. Such is the case when the internal diameter changes in a combination string of pipe, when seals of a slick joint assembly are subject to pressure and in the end effects of a tubing string. The change in tubing length due to the piston effects of a slick joint packer is affected by the various diameters involved, the tubing pressure Ap,, the casing pressure ,Ap,, length of pipe L, densities of fluid in the tubing before and during pump-

By E. M. Baroody

MUCH information on intermetallic diffusion has been obtained in experiments in which two volumes, initially at different uniform concentrations, are maintained in contact at an interface which is plane, or nearly so. Concentration-distance curves are obtained after suitable times, and analyzed on the basis of a one-dimensional form of Fick's law In early work the linear equation to which Eq. 1 reduces when D is independent of concentration was used. However, when the initial concentrations c, and c, are appreciably different this simplification is often unjustified, and the suggestion by Matanol in 1933 of a way of avoiding it was welcomed. Matano's paper was based on work done as early as 1882 by Boltzmann.2,3 In 1938 Rhines and Meh14 reported an extensive investigation of systems in which the diffusion coefficient depends strongly on concentration, and included a detailed description of the Matano-Boltz-mann method. To a large degree, this description represents the formal method as it is understood and applied today, most later discussions having emphasized thermodynamic and mechanistic aspects of diffusion. Exceptions are the comments of R. V. Churchill, contained in a paper by Ham, Parke and Herzig,5 and the papers by Hall8 and by Kirkaldy.7 More discussion appears necessary since some aspects of the problem remain obscure. Better computational procedures are also needed. The common method, involving graphical determination of slopes and areas, is inconvenient and makes the estimation of errors difficult. Background of the Matano-Boltzmann Method Eq. 1 is to be considered along with initial and boundary conditions. Take the origin of x at the

Jan 1, 1958

By C. Dinis da Gama

In mining, all unit operations are closely interrelated, and the results of blasting are probably the key factor within that sequence. The drilling program prior to blasting is just as dependent upon the desired rock fragmentation as are the loading, hauling, and mechanical crushing operations which are economically and technically influenced by the results of blasting, namely, the size and scatter of the product. What is known today as optimum blasting is the process of designing a blast in order to obtain a certain degree of fragmentation so that overall mining costs are minimized. Applying this criterion often results in a different program than when an individual blasting pattern is chosen only on the basis of the lowest operational cost for that pattern, disregarding what comes before or after the blast. [Fig. 1] shows the characteristic variation of mining unit costs with the degree of fragmentation, or the maximum size of blocks obtained from blasting. From the figure, it can be seen that optimum breakage must correspond to the lowest total costs, but reducing drilling-blasting costs only does not achieve such an optimum solution. Methods of designing surface or underground blasting operations should comply with the optimization criterion, but this compliance is feasible only if a detailed mining system analysis is available. Therefore, predictions of costs of loading, transporting, and mechanical breakage of ore as a function of its size will define a narrow range of variation for drilling and blasting parameters in order to get the minimum total costs.

Jan 1, 1972

By W. J. Nelson, R. B. Nance

Detailed underground geologic mapping at a scale of 1:1200 has been carried out at the Crown II Mine of Freeman United Coal Mining Co., which operates in the Herrin (No. 6) Coal Member. The roof sequence, upward from the coal, includes (1) soft, medium -to dark-gray shale; (2) hard, black, fissile shale; (3) argillaceous nodular- bedded limestone, and (4) fine-pined, shaly, water-bearing sandstone. The first unit is highly lenticular, and any or all may be missing at a given locality. The sandstone has a sheet facies and a channel facies. The Herrin Coal is eroded in channels near the Crown II Mine. Structural features mapped at Crown II include normal and strike-slip faults and limestone "bosses." Less stable roof and wet conditions are encountered where the limestone is thin or missing or where it is broken by natural fractures or by artificial openings that intersect the water-bearing strata above the limestone. Geologic mapping of the underground workings has allowed us to predict faults, fracture zones, and channels ahead of the face for this mine. Some lithologic and structural pattern apparently are random and cannot now be projected. Conventional exploratory drilling is entirely inadequate to map faults or lithology of the roof, but it does indicate the range of lithologic variability, which can be used to project needs for roof supports. Drilling also is useful in locating channels and in mapping regional variation in thickness and facies of the sandstone.

Jan 1, 1983

By J. M. Gaines, C. H. Herty

It is a matter of frequent record in the literature that manganese will desulfurize molten iron under proper conditions. Particularly has much been written with regard to this action in the mixer, and numerous reports have been published describing experiments in which advantage was taken of this phenomenon in order to obtain a purer iron for the open hearth. The question of sulfur elimination in the ladle has, however, received comparatively little attention. The reaction by which sulfur is removed is considered to be: FeS + Mn = MnS + Fe. The manganese sulfide, being but sparingly soluble in the iron, and of a lower density, will rise from the body of the metal and collect as a slag on the surface. It is therefore an action taking place solely in the metal, and independent of interaction between slag and metal. As will be shown later the presence of slag on the metal tends to offset the effect of manganese elimination. It is this fact which distinguishes desulfuriza-tion in the ladle from desulfurization in the mixer, for it has been shown1 that the amount of sulfur eliminated in the mixer is closely tied up with the composition of the slag. Experimental Procedure In order to ascertain the extent of and the factors controlling this elimination in the ladle, several casts were sampled carefully at the blast furnace and again when the ladles were being emptied, either at the mixer, open hearth, or foundry. If the sulfur content varied from ladle to ladle at the blast furnace the average sulfur content of each ladle was obtained by integrating the curve "sulfur vs. time " for the cast under

Jan 1, 1927

By W. R. Foster, J. M. McMillen, A. S. Odeh

The complete equations of average linear momentum balance for a single-phase fluid in an incompreisible, homogeneous, porous medium are derived. The derivation begins with Euler's equation of motion for a continuum and uses an integral transform recently developed by Slattery. 7 For steady flow of a compressible, Newtonian fluid, the usual equations of motion result. For transient flow, the space-time description of the pressure is determined in the lowest approximation by the telegrapher's equation. From the analysis a new phenomenological coefficient results which connects the viscous traction to the deriv ative of the linear momentum density. The magnitude of this coefficient determines the velocity of sound through the pore structure in this approximation to the pressure field. INTRODUCTION The modification of Darcy's law of momentum balance for steady, single-phase flow through porous media has been discussed for many years. The first modification was suggested by Forcheimerl who added terms of higher order in the velocity. These can be expected to appear because the underlying microscopic equations of momentum balance are themselves nonlinear in the point velocity field. The Reynolds tensor pvv, which represents the convective flux of momentum density, appears in the momentum balance equation. Only in rectilinear flow (parallel stream lines) does the divergence of this tensor vanish. Since the steady flow stream lines in most porous media are not parallel, nonlinear dependence of the pressure gradient on the velocity should naturally appear. This nonlinearity has nothing to do with turbulence in the ordinary sense of random fluctuations in the pressure and velocity fields. It arises simply because the stream lines converge and diverge, even for steady flows. Klinkenberg2 demonstrated that the permeability coefficient in Darcy's law depends on the absolute pressure or, alternatively, on the density field. However, because he neglected inertial terms of the Forcheimer type, his correction coefficient could not be represented by a constant but tended toward a constant as the velocity decreased. Forcheimer's and Klinkenberg's modifications can be combined in a rigorous way to account for both inertia and slip during steady flow. This will be shown in a future paper. The transient change of pressure in porous media has been described by the diffusion equation.3 This form results from eliminating the velocity and density fields from a combination of the equations of motion in the form of Darcy's law, the continuity equation and an equation of state. Fatt4 suggested that the cause of deviations from the prediction of the diffusion equation for pressure transients lies not in the choice of Darcy's law as the equation of motion but on the existence of dead-end pores which might invalidate the averaged equation of continuity. On the other hand, Oroveanu and Pascal5 noted chat the time derivative of the momentum density must be included in the equations of motion since this measures the local rate of change of momentum density. Their differential equation for pressure is the telegrapher's equation (neglecting gravity). However, their form of this equation predicts that the speed of pressure propagation through the pore structure is the same as that through the bulk fluid. M. K. Hubbert6 attempted a derivation of Darcy's law by volume averaging the Navier-Stokes equations. Since these equations represent momentum balance at a point within an open set of points containing the fluid itself, Hubbert's volume averaging cannot lead to tenns involving transfer of momentum between the fluid and the walls of the pores. Once these viscous tractions are lost by choosing a control volume containing only fluid, they cannot

By Rodolfo V. de la Cruz, Richard E. Goodman

Knowledge of the initial state of stress in rocks provides a key to the solution of many problems in rock mechanics. The initial state of stress is part of the basic data required for rational design of structures in rock, since its redistribution when engineering activities are conducted is a primary load on the rock portion of the engineering system. Knowledge of initial and subsequent changes in the state of stress is also relevant in the study of active faults and crustal strain. The purposes of stress measurements are not generally well served by methods which disclose only one of the stress components at a point. Recently, interest has centered on overcoring methods which though ex- pensive and difficult have the important advantage of yielding data on three or more stress components. In a previous paper, the authors introduced a new method-termed borehole deepening-based on measurement of the deformations that occur close to the bottom of a borehole when it is deepened by further drilling without overcoring.l The proposed method is at a disadvantage when compared with over- coring procedures in that the quantities to be measured are somewhat smaller and the measuring environment is more hostile. However, the borehole deepening method presents three distinct advantages in comparison with overcoring procedures: (1) Using the same borehole, both the initial and the subsequent changes in the state of stress can be obtained by borehole deepening. Stress changes with time are

Jan 1, 1970

Body Hoists A complete new line of hydraulic dump truck body hoists and bodies featuring many outstanding design improvements has just been announced by St Paul Hydraulic Hoist Fourteen models of this new hoist are available in a selection of capacities from 6 to 25 tons The new body hoist features low standard mounting height, advanced lifting point, new low operating oil pres [ ] sures, a new Uniflex subframe, friction-free roller bearing drive mechanism, including pump and power takeoff, to insure quiet operation and long trouble-free life A stress-eliminating design feature of the new hoists absorbs dumping shocks and permits use of a new principle in hoist design a flexible subframe which ends tendency of rigid hoists to crack or bend when flexed Circle No. 1 Combination Drill A new combination drill offering all three methods rotary, auger, and percussion drilling on the same rig is the revolutionary feature of the latest drill rig designed by Mobile Drilling Inc The B-36 drill is larger, more powerful and versatile than previous models built by this company This new drill has a hydraulic feed of approximately 8000 lb pressure The hydraulic feed cylinder is located directly over the rotary turn table The carriage of the drill is of tubular construction The drill mast, also of tubular construction, nests in the tube members of the drill carriage for cross-country travel with a maximum overall height of 10 ft The drill mast telescopes together with the feed cylinder hydraulically to an operating height of 16 ft The drill can be furnished with an auxiliary cat head, sand reel, and special high pressure water pump The B-36 maximum depth for auger drilling without water is approximately 150 ft, depth for rotary drilling with water is in excess of 300 ft Circle No 2

Jan 1, 1952

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf's CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

By E. J. Yoder, N. B. Aughenbaugh, R. B. Johnson

Mineral aggregates experience degradation during field and laboratory compaction. Reduction in the aggregate size is accomplished by abrasion of the particle edges and fracturing of individual pieces which have become overstressed. Little is known of the factors that govern the amount of breakdown experienced for a given situation. A field study was made of the factors affecting aggregate breakdown under compaction using three carbonate aggregates of different physical properties. The preliminary results indicate that rock type, compactive effort, gradation, and thickness of compactive layer are factors which exert the greatest influence. Mineral aggregates experience a mechanical breakdown of some of the aggregate pieces into smaller fragments during any compaction process, whether in the field or laboratory. This phenomenon occurs as abrasion of the sharp edges during movement and reorientation of the particles in densifying and/or as granulation and fracturing of those pieces which have become overstressed. Two types of aggregate breakdown occur in the field. These may be classed in a general category of aggregate degradation.* One occurs during the con- * Aggregate degradation has been defined in many different ways. For this paper it is considered as any breakdown of larger particles into smaller ones, whether mechanical or chemical. struction period and is related to the densification of the aggregate body from a loose state to a relatively dense mass by heavy compaction equipment. This type is almost entirely a mechanical action. The other occurs after the construction period when the roadway has been put into use. This in-service breakdown is; a different phenomenon from the breakdown during construction in the sense that it combines mechanical with chemical changes. Time becomes an important consideration that may cause subordinate factors in construction degradation to develop into principal ones for in-service breakdown. Breakdown of aggregates in service has been extensively studied by investigators from the northwestern

Jan 1, 1962