Search Documents

By R. W. Brauchli

The author has made a statistical analysis of the relations between recovery and length of cores, diameters of cores and of drill pipe, and cost of coring under different contractual conditions. The data are presented in tabular form. The length of the core appears to play a minor part in the percentage recovered, with a tendency to lower percentages with increased core length; approximately 50 per cent of the length cored is normally recovered if the cores are more than 2 in. in diameter. The diarneter of the core has a more pronounced influence on the recovery; 1 3/8-in. cores average 29.1 per cent, 2 1/8 -in. core 53.4 per cent and 3 1/8-in. cores with 6 5/8-in. drill pipe 68.5 per cent. Where 31/8-in cores were taken with smaller diameter drill pipe, i. e., 4 1/2 - in. drill pipe in 8 1/4-in. hole, the recovery dropped to 49.8 per cent, indicating that the more rigid drill pipe favors good core recovery, a conclusion also borne out by the results obtained in using large drill pipe for smaller diame-ter cores. Surprisingly good recoveries were obtained from both the Johnson and Simpson sands; shale, limestone and dolomite each gave less then average recoveries. No serious fishing jobs resulted from coring operations. Attention is called to the need of a core drill which will make it possible to drill a full-sized hole while coring, and thus reduce the cost of cores. Data pertaining to core drilling should be consistently recorded, such as, diameter of drill pipe and collar, diameter of core, recovery, size of cutter heads, type of core-barrel, coring time, speeds of rotation and of pumps, weight on core-barrel, etc.

Jan 1, 1933

By Ian W. Wark, Keith L. Sutherland

IT has been shown' that in the absence of heavy metal salts, the nature of the alkali used to promote differential flotation-whether caustic soda, lime or sodium carbonate-is unimportant. The hydroxyl ion is the active depressant upon which differentiation depends, and the pH value determines whether a film of collector forms on any given mineral surface. Even when sodium cyanide is used in conjunction with alkalies, it is the pH value and not the nature of the alkali or its concentration that is important, for upon the pH value alone depends the fraction of the added sodium cyanide that is present as cyanide ion, which is the true depressant. When heavy metal salts become dissolved from partly oxidized ores, or are added intentionally as activators, conditions are different, and metallurgists have found that lime and sodium carbonate do not give identical results, even when added in amounts sufficient to produce the same pH value. In the few instances in which we had attempted to confirm this view, we had failed to do so, for, with nothing to guide us, we had inadvertently chosen solutions that gave contact curves of a "standard type," which correspond to conditions of ready floatability. Now, however, we find that, in the presence of copper salts, and within a restricted range of reagent concentrations, the nature of the anions present is important, and that sodium carbonate does influence the results, apart from the usual effect due to its influence on pH value. With the recognition of this anion effect, and with the control of temperature already introduced,2 it appears that the factors of major importance in connection with this set of reagents have been taken into consideration, and that the results obtained and the conclusions drawn from contact tests will be of more immediate value to the operator. It is not difficult to suggest an explanation for the influence of the carbonate ion in the presence of copper sulphate. The works of Picker-

Jan 1, 1939

By W. M. Brown

SEQUACHEE Valley includes portions of the counties of Marion, Sequachee, Bledsoe and Cumberland. It extends in a general direction parallel with the Great Valley of East Tennessee, some 75 miles northward from the Alabama state line. It is separated from the Valley of East Tennessee by a mountain arm about a dozen miles wide, known as Wallen's or Walden's Ridge. The genesis of the valley, geologically speaking, is simple. It is an erosion-valley along the axis of an anticlinal. The point of the wedge remains in a row of low "saw-tooth" hills, running up the center of the valley. These hills are of Lower Silurian age, and consist of Trenton limestone, covered and protected in some measure by chert. Walls of Carboniferous age form the inclosing mountains on either side; whilst a magnificent arch of Hudson River, Niagara, Hamilton and Subcarboniferous strata closes the valley at the

Jan 1, 1886

By A. M. Gaudin, D. W. Fuerstenau

By streaming potential techniques, the zeta potential of quartz has been measured as a function of the concentration of dodecylammonium salts at different pH values. These experiments indicate that adsorption of dodecylammonium ions takes place as individual aminium ions until a certain critical concentration is reached in the double layer, at which point the adsorbed collector ions begin to associate into patches of ions, called hemi-micelles. Because of its effect on the surface potential of quartz, pH controls the adsorption of dodecylammonium ions. The value of cooperating agents and nonionized constituents of flotation systems is discussed. A PREVIOUS investigation' of the role of pH in the flotation of quartz with anionic collectors is here extended to an inquiry of how the cationic collector, dodecylammonium acetate, is adsorbed at the quartz-solution interface. The equilibrium amount of this collector adsorbed by quartz has already been measured as a function of concentration and pH.2,3 The weight of prior evidence has suggested that two mechanisms are involved in the adsorption of this collector by quartz, but with existing adsorption measurements alone it is not possible to determine what the mechanisms are. Gaudin and Bloecher2 postulated that a polymolec-ular adsorption coating begins to form before the first monolayer has been completed. Gaudin and Morrow4 indicated that a similar situation might exist in the film of dodecylammonium ions on hematite. A study of electrokinetic potentials at the quartz-solution interface provides some detail toward a fuller understanding of the adsorption mechanism. Experimental Results The zeta potential at the quartz-solution interface was calculated from streaming potential data measured with the apparatus described in detail in a thesis by Fuerstenau5 and briefly in a paper by Gaudin and Fuerstenau.1 The quartz used in these experiments was a 48/65-mesh fraction prepared in the manner described previously.' Zeta potential of quartz was obtained for various amounts of the amine salt at pH 4, 7, 10, 11. In

Jan 1, 1956

By Norman D. Fitz Gerald

THE growth of domestic requirements for motor fuel has been phe-nomenal, rising year after year in a fashion almost unique among com-modities, resisting depressions and forging rapidly ahead in times of prosperity. Consumption advanced from 226 millions of barrels in 1925 to 522 millions of barrels in 1938; or 130 per cent. The economic influ-ences generating and sustaining this demand are of vital concern to the petroleum industry. The general factors affecting utilization of motor fuel are well known but it is the purpose of this paper to employ the recently developed technique of economic dynamics to describe them mathematically. Such problems in economic analysis are complicated by the freedom of all the variables to fluctuate, their mutual interdependence, changing incidence upon one another, and the nonquantitative character of some of them. Economic quantities and relationships, unlike those of the physical world, are continuously changing and this dynamic characteristic is both a distinguishing and confusing feature in economic research. The com-plexities of the problems require application of the analytical devices of mathematical statistics to uncover the probable relationships between factors. The procedure employed is to formulate a logical relationship linking the dependent to the independent variables, and then simul-taneously, rather than sequentially, determine their separate effects by multiple correlation. This transformation of common knowledge to quantitative terms makes it possible to measure the probable effects of changing conditions upon requirements, assisting in the sound interpreta-tion of economic policies. The utility of the results of such dynamic analysis is in sharp contrast to the sterility of the trends and other simple empiricisms of descriptive statistics. It is not intended in this study to throw light on the reasons why any motor fuel at all is consumed; but to discover relationships explaining why more was consumed at one time than at another. Specifically the prob-lem is confined to the measurement of the influences of statistically

Jan 1, 1940

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By Jacob T. Wainwright

This stove has been designed to meet the requirements of a fur nave that must be operated with either a reducing or a neutral flame ; and more particularly to make feasible the operating of re duction-furnaces with the cheaper grades of gas-fuel, which has heretofore been impracticable. In general, cheap gas-fuels result from incomplete combustion, and, being suited for further combustion, answer very well for heat ing purposes; and high temperatures may be attained with them, when they are used in conjunction with regenerative stoves. But, in operating a reduction-furnace, a high temperature is not the only requirement. It is also necessary that the fuel shall not be cansumed beyond a certain degree, in order to insure a re ducing flame for the reduction-process ; consequently, it becomes necessary to dispense with combustion as much as possible previous to the use of the fuel-gases in the reduction-furnace. Moreover, these gases must be preheated to a high degree, in order that a sufficient temperature may be maintained in the furnace; and, since this preheating cannot be accomplished by a previous, partial combustion of the gases themselves, it follows that the stoves for pre heating these gases should be heated to as high degree as it is pos sible to attain with an inferior fuel. This result can best be accom plished by complete combustion of the heating gases, and is further facilitated by preheating all of the air and gas used for this com plete combustion. It is more particularly desirable to preheat the air, since the combustible gases used may generally be obtained directly from the furnace, or gas-producer. The reducing gases, escaping from a gas-fuel reduction-furnace, are capable of considerable further dilution with air to secure com plete combustion, and consequently may be utilized for heating the stove to a high temperature, provided the air be sufficiently preheated.

Jan 1, 1889

By Morris Muskat

In preparing a well for pumping, observations are often made of the fluid level in the well bore or bottom-hole pressures at various times before equilibrium has set in. From a qualitative point of view one may immediately infer that if the rise in the bottom-hole pressure or fluid level is rapid the permeability of the sand about the well bore is large, and converse conclusions may be drawn if the rise is slow. However, a more quantitative estimate will give additional information of value, as will be shown in this paper. To derive such an estimate we may proceed as follows. Let h be the fluid height, above the sand face, at time t, and let yo be the average density of the fluid that enters the bore. The bottom-hole pressure, for a fluid height h will therefore be p = rogh, neglecting, of course, the friction drop in the well bore, while the fluid is rising, as may be justifiably done for most pumping wells. If a is the free area of the open-flow string—assumed to be uniform— the rate of production from the sand during the rise of fluid will be: where the last part of the equation merely indicates that, in general, the production rate Q must be considered as a function of the back pressure, and is determined by it alone. In fact, equation 1 shows that if the rate of rise of the pressure or fluid level is determined as a function of the height of rise, or p, for a number of values of the latter, this functional relation between Q and p will be immediately given. Conversely, if we know this functional relation, the rate of increase of p or h may be predicted, or, by observing the rate of rise of p or h some of the constants of the sand may be determined. Thus we may approximate the production from a well in a pumping state by that of a dead

Jan 1, 1937

By Louis E. Reber

Jan 1, 1922

By F. X. Tartaron

This article is a continuation of a previous paper by the writer in which Kick's Law was stated to be a part of comminution theory. ln the present paper, a broadening of ideas is attempted in order to state a general theory. The word "general" is employed because the new theory includes all previous laws and generalizations which are considered to be essentially correct. These ideas are combined into a coherent whole and the general theory can be expressed by the equation In the author's previous paper on comminution, ' the equations developed were based on Charles' equation of exponents a-n +1 = 0. 2 This paper is divided into two parts, designated as First Approach and Second Approach. In the First Approach, the equations of the previous paper are utilized, with Charles' equation of exponents being necessary. In the Second Approach, a separate and independent method is used to derive the same conclusions as in the First Approach, but without the use of Charles' equation of exponents. Holmes accepts the theoretical foundation of Kick's Law as sound but denies that the law as such operates in comminution. His idea is that Kick's Law requires homogenous matter whereas the presence of cracks, flaws and cleavage planes, which predominate in the coarser particles, makes matter unhomogene-ous. This explains why there is no experimental evidence to support Kick's Law. However, since the basis of the law is theoretically sound, all experimental evidence must be viewed as emanating from it. This requires modification of current comminution equations to fit this concept. Holmes makes the modification by changing the constant exponent n in the general energy equation used by Charles (E = - JCdx/xn) to a variable exponent r. The writer asserts that Kick's Law operates in comminution without modification but it does not

Jan 1, 1963

UNIVERSITY OF ALABAMA University, Ala Mining and Metallurgical Society G T Bator UNIVERSITY OF ALASKA College, Alaska Mining Society Earl H Beistline-

Jan 1, 1952

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen' determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

IN THE past year, Jaffee and Campbell&apos; and Finlay and Snyder2 reported on the mechanical properties of titanium-base alloys, some of which were in the same ranges of composition as are covered in this paper. In this paper, evidence confirming that given by Finlay and Snyder on the effects of carbon, oxygen, and nitrogen on titanium will be presented; and, in addition, new data will be given on the effects of these elements on the flow properties and phase transformation of titanium. Materials and Preparation of Alloys The preparation and general properties of iodide titanium have been adequately described elsewhere.&apos; , As-deposited iodide titanium rod, prepared at Battelle, of Vickers hardness less than 90 was employed as the base metal in the present work. This was the same material as that used by Finlay and Snyder.2 The probable analysis reported by them for standard quality metal holds here also: N 0.005 pct, 0 0.01 pct, C 0.03 pct, Fe <0.04 pct, A1 <0.05 pct, Si <0.03 pct, and Ti 99.85 pct. Carbon was added in the form of flake graphite supplied by the Joseph Dixon Crucible Co. Oxygen was added in the form of c.p. grade TiO, powder, produced by J. T. Baker Chemical Co. Nitrogen was added in Ti3N4 powder, supplied by the Remington Arms Co. Individual ingots weighed 7 or 8 g. Carbon, oxygen, or nitrogen was added by placing the corresponding powder in a capsule made from as-deposited iodide titanium rods and melting the capsule with the balance of the charge. The charge was are-melted with a tungsten electrode on a water-cooled copper hearth under a partial vacuum of very pure argon (99.92 pct minimum). Melting was practically contamination free. Vick-ers hardness increases of less than 10 points were normal for unalloyed iodide titanium control melts. Nitrogen analyses of are-melted iodide titanium showed a nitrogen content of 0.005 pct, about the same as is present in the as-deposited rod. No tungsten pickup was found in a melt of iodide titanium analyzed for tungsten. Weight losses in melting nitrogen-free alloys were very small and varied consistently from nil to 0.015 g (0 to 0.2 pct). This permitted the use of nominal composition for these alloys. Chemical analyses made for carbon, which can be analyzed conveniently by combustion methods, justified this procedure. Where nitrogen was added, considerable splattering took place. Here it was necessary to analyze for nitrogen by the Kjeldahl method. The ingots were hot rolled at 850°C to about 0.045 in. thick. After hot rolling, the strips were descaled by mechanical grinding, and then given a cold reduction of 5 to 10 pct to insure a uniform thickness throughout the length of the specimen. The edge strips and the tensile strips were annealed in a vacuum of 1x10-4 mm Hg pressure for 3 1/2 hr at 850°C and furnace cooled. Methods of Investigation Hardness Measurements: At least five Vickers hardness measurements were taken using a 10-kg load on each sample in the following conditions: (1) top and bottom of each ingot, (2) top and bottom surface of as-rolled and annealed sheet, and (3) on cross-section of annealed sheet and all quenched specimens. Tensile Tests: Tensile tests were conducted on Baldwin-Southwark testing machines having load ranges of 600 or 2000 lb. Tests were made on 1-in. gauge-length specimens, 3 1/4-in. overall length, 1/2 in. wide, 0.040 in. thick, with a reduced section 1 1/4 in. long and 0.250 in. wide. Two SR-4, A-7 strain gauges, one mounted on each side of the specimen, were used to measure the strain over a limited range to determine the modulus of elasticity. After the modulus of elasticity readings had been taken, load vs. strain readings were taken, using only one strain gauge, at increments of 0.0001 in. until the yield points were passed and then at 0.001-in. increments to the limit of the strain-gauge indicator (0.02 in.). Strain readings above 0.02 in. per in. were taken every 0.01 in., using dividers to measure the strain between the 1-in. gauge marks until the maximum load had been reached. Crosshead speed, when using the SR-4 gauges, was 0.005 in. per min, and, when using dividers, 0.01 in. per min. Flow Curves: Flow curves were determined using the true stress-true strain data obtained during the tension test. The usefulness of this type of information has been dealt with very adequately elsewhere by L. R. Jackson,&apos; J. H. Hollomon,6 and many others. Flow curves of true stress vs. true strain could be converted to the more conventional cold-work curve of 0.2 pct offset yield strength vs. percentage of cold reduction by means of the transformation, 1/1 = 1/1-R, where R is the fraction reduction in cold working. Thus, the true strains corresponding to percentage reduction can be calculated, and the 0.2 pct offset yield strengths scaled off the — 6 curve by taking the true stresses corresponding to the values of 6 + 0.002 strain. Heat Treatment: For the transformation studies, the alloys were heat treated in a horizontal-tube furnace using a dried 99.92 pct argon atmosphere, and quenched into water. Essentially no contamination was found after several hours of heat treatment at temperatures up to 1050°C. Metallography: Specimens were prepared in the

Jan 1, 1951

By William M. Bowron

THIRTY years ago, when I stood on the cliff of red fossil iron-ore, on Red mountain, Jefferson county, Ala., I asked what were the geological relations of this remarkable deposit. In reply I was told that it was a limestone colored and saturated by some unknown but wholly external influences, and that at a reasonable distance from the surface the color would disappear. I could find no satisfactory explanation either of the nature of this wonderful external permeating influence, or of the cause of such a ferrous impregnation selecting this one particular bed of limestone, to the exclusion of the higher and lower beds of the same material which are not even stained. I. THE PRESENT THEORY. Referring to this subject, Dana says:&apos; "The clays, clayey sandstones and limestones of the Clinton epoch, through New York and the Appalachians, show that the mud-flats and sand-banks, and hence the shallow seas of the coast region, still continued. . . The beds of argillaceous iron-ore, which spread so widely through New York and some of the other States, south and west, could not have formed in an open sea, for clayey iron-deposits do not form under such circumstances. They are proof of extensive marshes, and, therefore, of land near the sea-level. The fragments of crinoids and shells found in these beds are evidence that they were, in part at least, salt-water marshes, and that the tides sometimes reached them." At first, this explanation seemed satisfactory, but the more I studied the ore the less satisfying the explanation became. 1. In the ore itself I found associated with the small particles of rounded matter (now consisting of iron oxide in which organic structure, if ever present, has become lost, though the

Nov 1, 1905

By C. M. Nickerson

IT is apparent that repressuring of the oil measures is becoming increasingly important to the oil industry, and is a matter that warrants the best efforts of the petroleum engineer charged with applying this method of operation to a producing property. Considerable attention has. been directed to repressuring in various California oil fields, such as Dominguez and Seal Beach, which have served to sell the more progressive operator on this idea and also to keep him sold. The projects that have received most attention are in comparatively young fields where the fluid levels are high, the wells, perhaps, still flowing, where the wet gas production is of considerable volume, and where there is vital need of immediate conservation of gas, which otherwise would be blown to the air. The new State of California Gas Law, which prohibits the waste of gas, has served to interest the oil industry in -means of conserving the gas that is now being blown to the air because of lack of markets. This vitally affects the operator in the older, well-depleted oil fields of the state, because in many cases he has a limited market for gas, on account of the flush production from the more active oil fields. While the waste of gas is relatively small in these older fields, such as the Midway-Sunset area, it now attains considerable importance, since under the new State Gas Law it must be put to some beneficial use. Repressuring in the older fields of California has not received the attention of the petroleum engineers that is warranted by the present situation. This paper was prepared with the view of presenting the salient features connected with repressuring in the well-depleted oil measures of the older fields, and to show what results have already been obtained in these fields by injecting the unmarketable. gas into the sands, particularly in the Midway-Sunset field in the San Joaquin Valley of California. Other projects in the older fields of the state offer some supporting data in this connection, such as the Shields Canyon and the Brea Canyon fields.

Jan 1, 1929

By G. V. Raymor, James T. Waber, I. Rex Harris

The lattice parameters of a series of fcc alloys of cerium and thorium were measured at 93 " and 298OK. Lattice parameters were also estimated for 171OK. Substantial deviations, y, from Vegard&apos;s law were observed. Although y was negative at the two higher temperatures, it was positive and large at the lowest temperature. A variety of models, which have been proposed in the past, were considered, and the calculated values of y were compared with the observed values. The best agreement was achieved with values computed with Friedel&apos;s equation. THE purpose of this investigation was to determine the effect of temperature on the lattice parameter and on deviations from Vegard&apos;s law of Ce-Th alloys. A large negative deviation from Vegard&apos;s law was first observed independently by Weiner, Freeth, and Raynor&apos; and Van vucht2 in the room-temperature lattice parameters of Ce-Th alloys that form a continuous series of solid solutions. This observation was confirmed by Evans and Raynor. The allotropy of unalloyed cerium was reviewed recently by Gschneidner, Elliott, and McDonald. In two subsequent papers,5" these authors reported the influence of various alloying additions on the y= transformation, which occurs below room temperature. Although other rare earths tend to stabilize the double-hexagonal phase, thorium, plutonium, and scandium as solutes tend to stabilize the normal fcc phase. With addition of sufficient thorium as a solute, there is evidence that the formation of is suppressed and it becomes possible to pass continuously with decreasing temperature from the room-temperature phase to the fcc a phase. Thus there is a closed loop which is similar in many ways to the y loop well-known in ferrous alloys. A closed field also occurs in the pressure-temperature "equilibrium" diagram of unalloyed cerium. Because of interest in the effect of thorium additions and their influence on the a and phases, lattice-parameter measurements were made at low temperatures on the fcc phase for a series of alloys ranging from 10 to 90 at. pct Th. The results obtained at three temperatures are shown in Fig. 1. Evans and Raynors analyzed the deviations from Vegard&apos;s law in Ce-Th alloys in terms of changes in the occupancy of the 4f electron level in cerium,

Jan 1, 1964

By J. H. Fletcher, S. M. Cassidy

Air has been cooled, heated, washed, humidified and dehumidified for many purposes and in many industries. At a number of metal mines air is conditioned to reduce the high humidity and unbearable heat found in deep workings, and at some mines air is washed to allay siliceous dust. Steam is introduced into the intake air at many coal mines, particularly in winter, for the purpose of keeping loose coal dust so moistened that the hazard of an explosion is lessened. This paper will describe a further successful application of air conditioning in a coal mine, where, for over three years, all intake air has been cooled to a constant temperature for the sole purpose of preventing roof falls. Effect of Warm Weather on Mine Roof It is generally known by mining men that some, if not all, coal mines have more trouble from bad roof during the warm summer months than in winter. Also, it has been observed that roof on intake airways is usually worse than on the return entries, after the air has circulated through the mine. Some mines and some coal seams are much more affected than others. In the Clinton district of Indiana, the No. IV coal seam has a good, firm, gray shale roof except during the summer months, when it deteriorates badly and falls in small slabs 1 to 6 in. thick. Timbering is not very efficacious during this period because in time the roof will shear around the supporting prop or crossbar and either dislodge the timber or leave it supporting only a few inches of crumbly shale (Fig. 1). This action is renewed each summer, choking airways with fallen slate, tearing down trolley wires, hampering haulage, endangering men and adding considerably to the deadwork cost. Only when mines have been worked for a period of years and have been advanced a long distance from the shaft do the active workings become comparatively free of this trouble, and even then the intake entries are still a source of much deadwork. Such was the annoying situation at the mine of the Saxton Coal Mining Co. operated in the No. IV coal just north of Terre Haute, Ind. During the months of warm weather it was possible to stand at any quiet spot in the mine and within 10 min. hear at least two or three falls,

Jan 1, 1931

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-&apos;. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.&apos; and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner&apos;s3 data for cation self-diffusion, D:, using Wagner&apos;s theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner&apos;s data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-&apos; at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970