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By Job Goostray

IN THIS paper, as in so many other discussions of historical nature, there is little chance for original material and much has had to be rewritten from older papers, documents, accounts, reports, and the like, some of which are of doubtful authorship or contain conflicting statistics. Fully aware of these little historical pitfalls, the authors have tried to quote the origin where possible, and also to seek further confirmation when the statement warranted it, but cannot assume responsibility for certain facts and dates. The Encyclopedia Britannica was frequently consulted. The authors wish to acknowledge assistance from MacKintosh-Hemphill Co.-formerly the Fort Pitt Works-and also from officials of the Watertown Arsenal who loaned valuable books and gave much necessary information. They are particularly indebted to Colonel Dixon of that institution. The data on modern guns were furnished by Mr. F. Brauer of the Watertown Arsenal; Mr. H. S. Chaffee assisted by obtaining records and data of work carried on by the Builders' Iron Foundry of Providence, R. I.

Jan 3, 1925

By A. Raman

The Nb-Co system was nuestigated in the range 10 to SO at. pct Co with X-rays. A pt phase with the W6Fe.r-type structure occurs in the system between 46 and 52 at, pct Co. Its unit-cell dimensions are nearly identical to those of the p Phases found in the Nb-Fe and Nb-Ni systems. Two Laves phases, one having the MgZnz-type structure and the other the MgCuz-type structure, already t-eported in the literature, are found to exist in the system. The ,l.IgZnz-type phase occurs between 62 and 64 at. pct Co. A MgNi2-type Laves phase, reported in the literature, is no! obtained. A binalry phase is found to exist belozv I000C around 82 at. pct Co. THE cobalt-rich side of the system Nb-Co has been repeatedly investigated by previous inestiators" and the following intermediate phases are known to occur: NbCo, which crystallizes in the MgCu2-type structure and Nbc03,' reported originally by Wall-bam, which has the MgNiz-type structre. Jordan and uwez' as well as lliott' were unable to find the MgNiz-type phase. Two phases, designated as x and y, were reported by Saito and eck.' The phase x was inferred to have a narrow composition range near 77 at. pct Co. No published work is known to the author which reports the investigations in the niobium-rich portions of the system. This paper presents the results of an investigation in the Nb-Co system between 10 and 80 at. pct Co. EXPERIMENTAL PROCEDURE Two or three grams of the alloys under investigation were prepared using niobium (99.9 pct +) and cobalt (98.8 pct + with 0.14 pct Fe and and 0.03 pct C) in a tungsten-electrode arc furnace under commercial argon atmosphere. They were then wrapped in molybdenum sheets and annealed for a period between 5 days and 1 week at 1300°C in high vacuum (10-" orr) or in evacuated quartz amules for 2 weeks at 1000°C. Powders of -325 mesh size were prepared for X-ray work by crushing and grinding the specimens. Subsequent reannealing of the powders was not undertaken since most of the alloys were brittle and broke easily. X-ray powder patterns of the as-cast and annealed samples were prepared in a Siemens cylindrical camera (57.3 mm radius) with Cr-K, radiation. A Siemens diffrac to meter was used to get the X-ray patterns of some new phases. Metal log raphic examination of the alloys supplemented the X-ray findings. RESULTS The results of the X-ray and microstructural analysis Of the alloys are in in Table I. The lattice parameters of the phases are listed in Table 11 for quick reference. A set of micro photographs in Fig. l(n) to (j) show the microstructures of some alloys. A probable equilibrium diagram is drawn in Fig. 2

Jan 1, 1967

F. E. Thompson, Pottstown, Pa.: If Mr. Webster's endeavor to open up the subject of cast-iron should prove as prolific of results as did the discussion on " The Physics of Steel," he must certainly feel richly repaid. His remarks concerning the secretiveness and conservatism of the average foundry-man recall to my mind an instance of a blast-furnace which, for the last year, has been producing much foundry-iron. The manager, believing that much more of his product could be used in the foundry than the foundry-men were will-

Jan 1, 1896

By Werner Ostertag

A series of rare earth cobalt compounds of the composition RCoa (r = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Ev, Tm, Lu) has been prepared. The compounds crystallize in space gvoup R3m and are isomorphous with PuNi3. Except for CeCo3 and PrCo, the series shows decreasing- values of a. and co. The relalively small parameters of CeCo, and PrCo, are explained by valencies of cerium or praseodymium which exceed the usual rare earth valency of three. The structure of the compounds is discussed as in-fillings of kagome nets in direct and staggered superposition. In the course of a systematic investigation of rare earth cobalt compounds"2 and their magnetic properties,, a series of alloys corresponding to the formula Rco3 has been prepared. The investigation of the Rco3 series was stimulated by our investigation of the yttrium cobalt system2 as well as by reports in the literature: Smith and Hansen4 reported the structure of YcO3 and Van vucht5 that of GdCo3; ceco3,6 Gdco3,7 and DyCo3 7 have been found to be single-phase during phase diagram studies. It was the purpose of this work to report crystallographic data on the entire Rco3 series and to interpret the structure of these compounds on the basis of general principles as discussed by Frank and Kasper.8 At the time this work was terminated, it was learned that a similar investigation has been carried out independently by Bertaut, Lemaire, and schweizer.9 Except for CeCo3 (ao = 4.952, co = 24.73') and NdCo3 (a0 = 5.067, co = 24.76') data of this work are in satisfactory agreement with their investigation. EXPERIMENTAL TECHNIQUES A series of samples having the composition Rc03 was prepared from stoichiometric amounts of the rare

Jan 1, 1968

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By Paul Berggreen

LIST OF PUBLICATIONS In the Bibliography titles of publications are replaced by corresponding symbols in this list. American A-1. Transactions of the American Institute of Mining Engineers, New York. A-2. Journal of the New York Microscopical Society, New York. A-3. Journal of the Franklin Institute, Philadelphia, Pa. A-4. The Metallographist, Boston, Mass. A-5. The Electrochemical and Metallurgical Industry, New York. A-6. Bulletin of the American Institute of Mining Engineers, New York. A-7. The Iron Trade Review, Cleveland, Ohio. A-8. The Journal of Physical Chemistry, Ithaca, N. Y. A-9. The Physical Review, New York. A-10. Van Nostrand's Electric Engineering Magazine, New York. English E-1. Proceedings of the Institution of Mechanical Engineers, London. E-2. Journal of the Iron and Steel Institute, London. E3. Proceedings of the Institution of Civil Engineers, London. E-4. Journal of the Chemical Society of London, London. E-5. Philosophical Magazine, London. E-6. Proceedings of the Royal Society of Edinburgh, Edinburgh., E7. Carnegie Scholarship Memoirs, London. E-8. Proceedings of the Royal Society of London, London. E-9. Chemical News, London. E-10. Philosophical Transactions of the Royal Society of London,, London. E-11. Transactions of the North-East Coast Institution of Engineers and Shipbuilders, Newcastle-on-Tyne E-12. Iron, London. E-13. Nature, London. E14. English Mechanic and World of Science, London.

Jan 6, 1914

By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By M. M. Singh, J. W. Brown

Three rocks of highly varied physical properties are selected for the first reported experimental study concerning microseismic activity of rock under tension to determine the effects of static fatigue, loading rate, repeated loading and rock anistropy compared to compression and bending loads. The microseismic method of detecting rock under deformation may be a great potential tool in surveillance and location in situ of dangerously stressed strata, as well as predicting rock failures. Noises emitted under load or the rate of energy (energy of noise pulses generated per unit time) are computed for varying conditions. The tests are conducted at constant load on a dead weight loading machine to eliminate all possible extraneous noises — an indispensable precaution — at various load levels. Experimental results are reported including the relation of total energy emitted to tensile strength of rock and the possibility of simulating a phenomenological model for microseismic activity. Plots of some of the experiments are included. INTRODUCTION Rock failure, whether on a large scale faulting in the earth's crust and rock bursts in mines, or on small scale ruptures of laboratory test specimens, generates transient vibrations in the rock mass. Mechanisms of intermittent deformation, such as twinning and cracking through and between mineral grains, also produce similar vibrations, but of very small amplitude. Such vibrations from both deformation and failure are referred to as microseismic activity, rock noise, or occasionally seismo-acoustical activity. An individual rock noise is sometimes

Jan 1, 1967

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By R. F. Nielsen, R. G. Bentsen

Jan 1, 1966

By P. T. Allsman

INTRODUCTION The honor of being the recipient of the Mining Society's Daniel C. Jackling Award for 1966 imposes on me the responsibility to search for the subject that I would be best qualified to discuss. It seems that my experience in the mineral industry — nearly 15 years in private and 30 years in public employment — should uniquely qualify me to comment upon the relationships between the mining industry, mineral engineering as a profession, and government, and the changing economic, technologic, political and social changes that dictate their relationships. Such conditions, the increasing knowledge of the world mineral resource base, the greater demands of an expanding population with a rising standard of living, shall be evaluated with respect to our profession — mineral engineering. In all of these forty or so years, I have been in close touch with many phases of the mineral and energy resource industries, especially those of the United States. Particularly during the past 10 years, I have had a ringside seat at the "goings on" in Washington. During all of this period I have observed and analyzed many of the problems of the industry and its relations with the government. During the past few years, I have had increased opportunity for doing research and have found a need to learn something about the mathematical techniques that are undergoing such a revival since electronic computers were developed. One of these techniques is multivariate analysis, which is a system for correlating a large number of complex variables. By applying this technique to the seemingly chaotic present-day situation, there emerges a course of steady improvement in the minerals resource industries that wars, depressions, and political strife have failed to obstruct for long. In short, I advocate a need for new concepts in mineral engineering to cope with the changes, pos- sibly adding many more specialized areas on one end of the spectrum, and broad engineer-generalist approaches at the other. The meeting place shall be where the intricate mineral resource problems at the frontier of knowledge merge into the socio-techno-logical problems of the world. HISTORICAL INVOLVEMENT OF GOVERNMENT IN MINERAL RESOURCE PROBLEMS Involvement of government in mineral resource problems undoubtedly is as old as government itself. But passage of the Mining Act of 1866, superseded by the Act of 1872, was the first major entry of our Federal Government into the problems of mining. Passage of the law was necessary to resolve many conflicting claims and disputes in mining. The General Mining Law of 1872 and the Mineral Leasing Laws of 1920 apply to millions of acres of public lands and to certain privately owned land on which the mineral rights have been reserved to the Federal Government. The extensive involvement of government in the mineral industry business today often comes as a shock to the mineral engineer who has begun to climb the ladder to the top in his company. He is often poorly prepared to cope with the situation and becomes frustrated and even hostile. Better knowledge of the role of government perhaps would ease his situation. In our political system, private industry is responsible for producing minerals. To make certain that the production is adequate for a peace-time economy, and to guarantee the Nation's security in an emergency, the Federal Government finds it expedient to develop policy and engage in regulatory, educational, and research activities. A few examples will illustrate the varied role of government in relation to mineral problems. In varying degrees many agencies of the Executive Branch of Government have responsibilities that influence the functioning of the mineral and energy industries. In addition, of course, Congress, the Judiciary, and State and local governments exercise great influence. The Department of the Interior is primarily responsible for activities to promote the development and conservation of mineral and fuel resources, and the

Jan 1, 1967

By H. J. Gerritsen

From presently available components a portable, rugged, reliable apparatus can be built which will be able to detect methane concentrations of 0.1% and lower in air. Sensitivity and design considerations of the apparatus are given. Ways to build even simpler and cheaper apparatus in the future are indicated. Traditionally the problem of detecting and monitoring the presence of dangerous gases present in small concentrations in air has been a difficult one. Whether canaries,' or sophisticated chemical or thermal conductivity methods are used, they seem to be either slow, cumbersome, or otherwise not completely satis factory. A seemingly natural way of gas detection is to measure the strength of absorption undergone by light of a wavelength that the gas to be detected absorbs. This method has been difficult to apply in view of the low power output over a narrow wavelength range in the infrared from traditional glow bar light sources. Besides, the apparatus to select such a narrow band of wavelengths is quite costly and complex. The use of a laser solves these problems simultaneously. Although a variety of lasers are available to detect a variety of gases (such as carbon monoxide or methane) whose early detection would be desirable, this paper deals exclusively with the use of lasers for methane detection. ABSORPTION SPECTRUM OF METHANE IN AIR The absorption spectrum of pure methane is very well known.2-4 There are four fundamental vibrations, all occurring in the infrared of which only two absorb strongly. They occur at 3.3 µ and 7.7 µ. The absorption spectrum is quite complicated due to the fact that the methane molecule can rotate in a variety of rotational quantum states. These rotational states are furthermore split by anharmonic forces such as the Coriolis force.4 When methane is present in air at atmospheric pressure, much of the very fine structure due to the anharmonic force is washed out since the pressure broadening is of the same magnitude as the splitting due to anharmonicity. For most of the spectrum at 3.3 µ, the rotational lines are typically separated by 0.01µ while the individual linewidth is 0.0001 µ. It is thus very important that the laser emit at a wavelength that coincides with one of these rotational lines. Before elaborating on the point that such a laser exists and how it performs, it is necessary for later discussion to point out that in the

Jan 1, 1967

By Potts N. L., Eilerts C. K., Summer E. F.

The second-order, nonlinear, partial- dillerential equation representing the transient radial flow of gas - condensate fluids in reservoirs has been integmted by using finite -dillerence equations and electronic computers. Effect was given to pressure -dependent permeability, viscosity, and compressibility and to distance-dependent permeability. The influence of a second-degree velocity term in the Darcy equation was investigated. Implicit methods were used and practical, convergent solutions were obtained with material balance to less than 6 x 10-4 for recovery of one- hall the reserve at constant flow rate. Integration results provide the productive period of a reservoir for a given constant rate and the fraction of the fluid initially in place that can be recovered in that period. The properties of a lean and a rich fluid are represented in a set of integrations designed to demonstrate the effect of different constant-recovery rates and significant variables emphasized one at a time. INTRODUCTION A method is needed for computing the availability or reserve of a gas in a formation, making use of all technical and engineering information that is pertinent. As a step in this direction, a program for computing transient linear flow1 was developed that utilizes principles of earlier finite-difference computing for a similar purpose2-4 and gives effect to significant pressure- and distance-dependent properties of reservoirs and their contents. The present paper pertains to transient, radial flow of gas-condensate fluids. In the partial-differential equation of flow, effect is given to the variables viscosity and compressibility,5 and also to permeability. Included in the study is the quadratic form of the Darcy equation of flow that has been the subject of field tests6 and that has been applied to a gas with constant properties in transient flow computing. 7 Inclusion in the differential equation of variable coefficients to represent properties greatly complicates the higher derivatives of the equation. Because it was impractical to make a required improvement in certain of the finite-difference derivatives by Taylor-series expansion, five-term derivatives were used in the implicit computing. Related methods were developed that can improve general facility in manipulating finite-difference equations. BASIC EQUATIONS PARTIAL DIFFERENTIAL EQUATION The basic partial differential equation for transient radial flow in the direction of decreasing radius is l_ a(vpr) _? .......(1) r gr at where r = radius, L v = apparent velocity aIong radius, L/t p = density, M/L3 t = time, t Ø = porosity, dimensionless. In this equation, only the porosity is regarded constant. The density is where p = pressure, m/Lt2 M = molecular weight of fluid, m T = constant temperature of fluid, T z(p) = pressure-dependent compressibility factor, dimensionless R = gas Constant, mL2/t2t. The physical boundary of the reservoir is at re, and the producing boundary is defined to be at tq with rq = re /200. By definition,

Jan 1, 1966

By J. R. Kyte, L. A. Rapoport

The material balance equation for partiai or complete 1:trter-drivc reser1,oir.s been re-arranged to include a pressure irrferferencr ternr. This pressure interfernce term was ohtained from the theory established hy Morinda. A .successful progranl deissed to solve the resrclritlg c,qrration in a few hours on a nleelitr .sizeti, digital compuier. No prior knowdelge of the properties of the eqrrifer is required in the solution. 7' ri~rl calculations areatle using various assumed con!binuiions of value of the constant expretsing the qquifer properties correspoinds to the best fit ohtained between observed and calculated field history. Details of the method of calculaion are illus trated by an example. INTKCDUCTICN A method 01' calculating the material balance equation for a partial water-drive reservoir completed in an aquifer has been described in the literature." Pressure interference i'rc,m other pools iocated in the same nquiucr is not taken into account in this solution. When present, the pres- sure interference effect must be included in order to make a complete performance analysis. A correction for this effect has been developed using the theory cstahlished by Mor-tada.' Manual calculation of the material balance for water-drive reservoirs is a formidable task. Such manual ca1culation when interference eflects are includcd would be impossible to completc in any reasonable time period. However, a medium-sized stored program, digltal conlputer can he used satisfactorily. The method is described in the following sections. THECKETICAL CONSIDEKATIOhS The material balance equation for a reservoir producing by partial or total water drive, as proposed by Van Everdingen, This relationship is linear for Z/a from which thc slopc, Z, and the intercept, N, can be obtained by the least-squares method from the data points. It is not necessary lo know the aquifer properties to uktain oplimum values tor 2nd IV. Various assumptions are made tor At,,: where 11 is production time, seconds (oilfield between the equal successive time intervals into which the history is divided. t,, h It, times the number of equal time periods from i.e.. the total dimen-sionless time interval from It is noted that the dinlensionless time interval, At,,, involves all the relevant aquifer properties. Accordingly, any assunlption of is an assumption of the combined aquifer properties which pertain to the solution of the equation. Deviations of the data points from a straight line arc calculated for each assumption of and the value of A, correspond ing to the minimunl deviation is chosen as the optimum solution. This method is described in Ref. 1 and 2. Thc material balance solution is usually made with an initial assumption that the reservoir being studied is located in an infinite aquifer from which there are no other withdrawals. Deviation of the points by amounts greater than can be attributed to inaccuracies in field data may be the result of: (1) boundary effects of a limited aquifer, (2) pressure interference from othcr pools completed in the .sarne aquifer, and (3) a combination of these effects. Differentiation of these effects can be made only on the basis of geologic data. Pressure interference from other fields will result in a pressure drop at the original oil-water boundary having an interference component, The measured instantaneous pressure drops at the oil-water

Separates of all the Technical Publications published in 1931 are available at Institute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found in the Transactions. Copies of these papers have been mailed to those members of the Institute who are registered in the different classes: A-Metal Mining; B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy; E-Institute of Metals Division; F-Coal Division; G-Petroleum Division; H-Nonmetallic Minerals; I-Mining Geology; K-Mining Administration; L-Geophysical Prospecting. Other members may obtain copies by writing to the Secretary. Additional copies are sold at the rate of I cent per page; minimum charge, 25 cents. Metal Mining Tech-nical Publi- Title Author Meeting TRanb. cation Volume No. and Page* 411-A.43 Ventilation at the Portovelo Mines, J. P. Harmon New York. T31, 83 Ecuador (18) Feb., 1931 425-A.44 Use of Models for the Study of Mining P. B. Bucky New York, Problems (28) Feb., 1931 Milling and Concentration 375-B.32 Ball Mill Studies, I (53) A. W. Fahrenwald New York, H. E. Lee Feb.. 1931 401-B.33 Experimental Flotation of Oxidized H. S. Gieser New York. Silver Ores (9) Feb., 1931 410-B.34 Flotation of Minor Gold in Large-scale E. S. Leaver New York, Copper Concentrators (32) J. A. Woolf Feb., 1931 414-B.35 Effect of Particle Size on Flotation A. M. Gaudin New York, (23) J. 0. Groh Feb., 1931 H. B. Henderson 416-B.36 Ball Mill Studies, 11.—Thermal A. W. Fahrenwald New York. Determinations of Ball Mill Effi- G. W. Hammar Feb., 1931 ciency (13) H. E. Lee W. W. Staley Iron and Steel Division 38QC.59 Open-hearth Steel Process as a Prob- E. R. Jette New York, C31, 80, 111 Iem in Chemical Kinetics (34) Feb., 1931 381-C.60 Thermodynamic Study of the Phasial Yap, Chu-Phay New York. Equi1ibriain the System Iron-car- Feb., 1931 bon (26) 382-(3.61 Influence of Dissolved Carbide on the Yap, Chu-Phay New York, Equilibria of the System Iron-car- Feb., 1931 ban (19) 383-C.62 Research on Blast-furnace Slags. R. S. McCaffery New York, Three papers (88) Co-workers Feb., 1931 384-C.63 Statistical Analysis of Blast-furnace K. S. McCaffery New York, C31, 60, 70 Data (13) R. G. Stephenson Feb., 1931

Jan 1, 1931

By J. J. Predali, J. M. Cases

J. J. Predali and J. M. Cases (Attachè de Recherche and Charge de Recherche, respectively, Centre de Recherches sur la Valorisation des Minerais, Institut Polytechnique de Nancy, Nancy, France)-The role of CO, in carbonate flotation is one of the parameters of a complex phenomenon: the adsorption of salts of fatty acids onto minerals. The authors therefore must be congratulated for their work. Their experimental results suggest some questions: 1) Recovery with C02, benzoic acid, or HCl, look very similar [(Fig. 1)] to that with the use of air; however, the recovery decreases very slightly (<10%). But in these two kinds of experiments, two parameters are different: the pH which is near 5.8 (with C02) becomes 9.1(without C02) and the concentration of Ca* I x 10-3 mole per 1 (without C02) becomes 1.9 X 10&apos; mole per 1 (without COO. 2) Adsorption experiments (Fig. 2) permit computing the surface coverage 9 which is 7.4% (without C02) and 8% (without CO_.) for an initial concentration of 12 X 10-6 mole per 1 in sodium oleate. It seems doubtful to us that this small variation can produce large increases of the recovery in flotation. 3) It is difficult to correlate adsoption and flotation experiments because they do not seem to have been done with the same size of particles. The concentration needed to obtain 95% recovery (Fig. 1) is about 3.0 X 10_" mole per l, that is, 1.13 X 10-6 mole for about

Jan 1, 1973

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken&apos;s Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3&apos;&apos;* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By J. W. MacDonald

Review of equipment, performance, and shaft design plans including head-frames for sinking and forms for lining are given. Also included are comparative data for shafts of 11 x20 ft and 193/4 x 30 ft with 756 and 666-ft depths, respectively. Advantage from curtain wall installation with "slip forms" which warrant consideration for normal lining are outlined. A preliminary review is also made of "chemical grouting" to stop water inflow leakage with Halliburton equipment and service. Two coal mine shafts recently completed in Franklin County, Ill., afford experience and accomplishment to warrant review. These shafts provide access to a tract with a potential recovery of one hundred million tons. This work provided the initial sinking by other than a contractor&apos;s organization since 1918. Four additional shafts required during the interim were sunk under contract arrangement with others. Supervisory contact and inspection afforded experience to govern planning and conduct of the recent work. TEST DRILLING Core test holes were drilled within each of the two shaft locations. Four additional cable tool holes were drilled on a radius of 700 ft from the shaft bottom to determine the coal seam elevations and govern the underground layout plans for each shaft. A graphic log of the hoist shaft test drillhole is shown by Fig. 1. A very soft sandstone was found at a depth of 16 ft. Cored recovery of the sandstone proved much weaker than the overlying compacted sand secured with coring facilities for soil recovery. Gradation from the very soft sandstone to fairly hard material occurred with the next 14 ft, extending to a depth of 30 ft. The weak character within the upper portion entailed need of adequate protection when sinking as described later. A part of the sandstone provided sufficient porosity and permeability to warrant further investigation. Adjacent cable tool drilling for temporary water supply disclosed inflow was limited to 2 gpm with a depth of 40 ft. It was increased to 12 gpm during the next 50 ft of drilling and occasioned subsequent precaution when sinking. General arrangement of facilities for sinking the hoist shaft is shown by Fig. 2. An available steel frame building was used to accommodate the hoist, compressor, shop, and shower or change room. The stiff leg derrick with 90-ft length of boom permitted removal of forms from the wood shop to the storage area or delivery within the shaft. Reinforcing steel and other needs were similarly handled, in addition to headframe erection. The headframe was placed over one end of the shaft to enable passage of forms for lining through the adjacent half next to the stiff leg derrick. The steel headframe as shown by Fig. 3 was fabricated locally. Side anchored cables from the

Jan 1, 1961

By G. P. Marino

The "conductivity ", Kr, of a spherical void in a linear temperature gradient due to radiation is calculated by integration of the general expression for diffuse radiation between two gray surfaces of arbitrary orientation. The spherical geometry allows an exact evaluation of the phenomenon without resorting to up-proximate expressions for the radiant heat flux. The resulting expression for Kr is three quarters of the approximate value obtained by Loeb. IN the determination of the thermal conductivity of porous materials such as sintered UO2 and ThO2 fuel pellets, the magnitude of the thermal conductivity in the pores due to radiative heat transfer across the pore, Kr, may be important in assessing the total conductivity of the pellets. Loeb&apos; has calculated Kr for various pore geometries by approximating the net flux of heat between two surfaces of temperature difference AT as 4eT~AT and obtained: K,=4yoet3odp [1] where a is the Stefan-Boltzmann constant, E is the emissivity of the radiating surface, To is the average absolute temperature of the region across which radiation occurs, dp is the largest dimension of the gap in the direction of heat flow, and y is a geometric factor. That is: y = 1 for laminar pores and cylindrical pores with axes parallel to the heat flow direction, y = 2/3 for spherical pores, y = /4 for cylindrical pores with axes perpendicular to heat flow direction. It was the purpose of this work to obtain an exact expression for K, in spherical pores by integration of the general expression for the net heat transfer between two incremental areas on the surface of a spherical pore. This procedure yields a value of Kr 3/4 of that obtained by Loeb. I) CALCULATION OF Kr Fig. 1 illustrates the general geometry which defines the problem. The total emissive power for a gray body is given by: E = EoT4 [2] where E is the radiated energy per unit area of the radiation surface per unit time, T is the absolute temperature, o is the Stefan-Boltzmann constant (o = 5.67 X lo- &apos;&apos; watt per sq cm-"K1), and E is the emissivity of the surface. Although Eq. [2] gives the exact expression for the total emissive power of any gray body, all practical problems involve the net exchange of thermal radiation between a body and surrounding bodies. The two major considerations in the solution of such problems are a) shape and relative position of the surfaces and b) the emissivities of the surfaces. In this work it shall be assumed that all incremental areas on a pore have the same emissivity and, further, that little or no reflection occurs (i.e., the radiation hitting a surface is either absorbed or transmitted). Thus, the solution of the stated problem requires only that consideration a be satisfied. Consider two incremental surface areas dA 1 and dA2 of the same material in a general orientation to one another. Let dAl be at temperature TI and dAz be at T2. Fig. 2 illustrates the geometrical parameters involved. That is, 71, is the normal of dA, n2 the normal of dA2, r the line connecting the centers of each area, 81 the angle between nl and r, and Q2 the angle between 7,2 and r. Using Eq. [2] and the Lambert cosine law of diffuse radiation it is easily shown that:293 WdAf- dA, = ecr T*------^fpi------" dAidA2 [ 3a 1 and

Jan 1, 1970