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By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By E. Lifshin, R. E. Hanneman

QUANTITATIVE applications of the electron micro-beam probe frequently involve the evaluation of complex mathematical expressions and/or the analysis of large amounts of experimental data. The purpose of this communication is to describe briefly a versatile and useful computer program system that is applicable to analyze rapidly a wide variety of practical microprobe problems. This system consists of a group of ten FORTRAN programs that can be stored on tape, cards, or in the memory disc of the computer. These programs, or links, can be run individually or in any prespecified sequence without interrupting the operation of the computer or without destroying information which is being transfered from one link to another. For the program system described here a GE-235 computer with disc storage was used, so that the DCHAIN method of program linking was employed. Included in the library are programs to: 1) initiate analysis of a new set of data and transfer control between all other programs in any predetermined manner; 2) generate theoretical calibration curves of composition vs relative intensity; 3) generate empirical deviation parameters from least-square fits of experimental calibration data from standards of known composition; 4) convert raw X-ray data to corrected composition; 5) determine inter diffusion coefficients by Matano analysis of con centrat ion -distance data on a uniaxial diffusion couple; 6) determine activation energies and frequency factors of temperature-activated processes such as diffusion; and 7) generate calibration curves for determination of the thickness of thin films using microanalysis. A detailed description of these computer programs and their underlying principles is available on request from the authors."' The first program to generate theoretical calibration curves of corrected relative intensities vs composition uses the Poole and Thomas atomic number correction' and the Philibert absorption factor' with a voltage-dependent mass absorption coefficient for electrons in the alloy. A modified Castaing fluores- cence correction is also used which includes the effects of both Ka and KO radiation and over voltage.' Once the theoretical curves have been calculated in 1 wt pct intervals, these results are least-squares fit to obtain Ziebold deviation parameters' which are stored in COMMON in the computer memory. The net discrepancies between the original theoretical calibration curve and the regenerated curve using the Ziebold parameter are computed. Although this link is explicitly written for K-K fluorescent interactions, it can be applied to K-L, L-K, and L-L interactions as previously disc~ssed."~ Similar programs have also been written to utilize the Wittry fluorescence correction, Birks combined corrections, and various other corrections.' These modified programs have proved to be quite useful for quantitative comparisons of the results of the various theories. The program for conversion of raw X-ray data to corrected composition includes corrections for drift, backround, and instrumental dead time. The corrected intensities are converted to composition by use of the Ziebold equation"2 and parameter obtained from the program system. The results can be obtained for either atom or weight fractions. In addition to accurately computing interdiffusion coefficients the Matano analysis program calculates least-square smoothed values of concentration, concentration gradient, and curvature for each point on the raw input concentration profile. In order to obtain high accuracies a unique method of performing a least-square polynomial fit to incrementally advancing profile segments which overlap is used.' This program has been successfully modified for use in ternary diffusion problems3 and can readily be modified to handle analysis of diffusion profiles which include phase boundary discontinuities. This link is generally applicable to analysis of interdiffusion data obtained by other techniques as well as by the microprobe. The primary function of the next program is to least-squares fit experimental diffusion data to the normal Arrhenius function: D = Doexp(-Q/RT), to obtain values of Do and Q. In addition the probable error and one, two, and three u statistical confidence limits of DO, Q, and log D are evaluated. This program is also directly useful for analysis of any other simple temperature-activated processes including conductivity, and certain deformation and chemical processes. The program to generate calibration curves for film-thickness determination using the microprobe is based on a numerical integration of the equation derived by Cockett and ~avis.' Values of film thickness obtained by this program for copper on various substrates are in good agreement with measurements made by other techniques. Versions of the above program system have been prepared for use with or without a remote teletype connection to the computer for processing on either a real-time or time-share basis. The instrumentation coupling a microprobe to a teletype for automatic data collection and analysis by the presently described program system has been reported elsewhere by the authors.' If teletype equipment is not used to communicate with the computer, standard methods of card reading and tape reading can be used. In either

Jan 1, 1967

By E. B. Brauer, W. Hurst, J. D. Clark

Because of drilling, completion, and workover practices, the permeability around a wellbore generally is different from the permeability of the formation. The zone with the altered permeability is called "skin" and its effect on the pressure or flow behavior of the well is called "skin effect". Hawkinsl has shown that the radius and the permeability of this zone are related to the skin by: If the permeability in the skin zone is less than that of the formation, the skin is positive; if it is more than that of the formation, the skin is negative. If the two permeabilities are equal, s is zero; that is, there is no skin. Van Everdingen2 and Hurst3 have given mathematical solutions to the case of a zone of reduced permeability around the wellbore. This skin effect is illustrated in Fig. 1. They treat the positive skin as a zone of reduced permeability of infinitesimal thickness around the wellbore. When applied to a well with negative skin, however, their solutions lead to the calculated flowing well pressure which is smaller than the formation pressure, i.e., an injection situation. This is a physical contradiction. In this paper, it is shown that this mathematical difficulty can be overcome by assuming an effective wellbore radius larger than the actual wellbore. Existing solutions2"4 are modified to include the effect of an enlarged wellbore radius, and thus enable the engineer to deal with negative as well as positive skins. Theoretical Development Van Everdingen and Hurst,4 through the use of Laplace transformation, obtained the following expression for transient fluid influx into a wellbore: The values for QtD, reported extensively by van Everdingen and Hurst,4 are obtained from the following integral:

Jan 1, 1970

By James B. Cathcart

The potash mine of the International Minerals and Chemical Corp. is about 18 miles east of Carlsbad, New Mexico, in sec 1 and 12, T 22 S, R 29 E, N.M.P.M. Potash is produced from two zones in the Salado formation of late Permian age. The lower zone, consisting of a mixture of sylvite (KCl) and halite (NaCl), lies at a depth of about 900 ft, and the upper zone, in which the principal potassium mineral is langbeinite (K2S04.2MgS0d), lies at a depth of about 800 ft. Because of the plastic nature of the material, fractures in the Salado formation are extremely rare and have been noted only on the 800 ft level of the International mine. The open fracture described below is almost unique. Only one other open fracture has been noted, and it was on a working face in the same general area as the one described, but was destroyed before the writer had a chance to examine it. According to J. E. Tong, foreman on the 800 level, this fracture was similar to, but smaller than, the one herein described.

Jan 1, 1949

By C. S. Barrett

It has been observed that deformation in iron takes place by slip on (110) + {112) + (123) planesl, 2, but in silicon ferrite with low deformation temperatures or high silicon contents (exceeding 4 per cent) the authors have found that slip is confined wholly to (110) planes, at least with small amounts of deformation. The purpose of the present investigation was to determine the effect of this alteration of slip mechanism on preferred orientations in cold-rolled and recrystallized strips. Incidental observations on the effect of the recrystallization temperature were also made. The numerous determinations of the texture of cold-rolled iron and steel have been in satisfactory agreement as to the principal features of the texture (with the exception of a few conclusions that apparently have been based on insufficient data). The texture is chiefly one in which 11101 directions of the grains lie along the direction of rolling, with a deviation of a few degrees, and in which the (100) planes lie in the plane of the rolled sheet, with a deviation from this position chiefly about the rolling direction as an axis. This deviation about the rolling direction as an axis has been measured by different observers and lies between about 45" and 50" or 60" for iron5, 6, 9 and is usually in the neighborhood of 50" for mild stee16, 7, 8. The range of this deviation is a function of the percentage of total reduction8, 10. Post8 reported that it decreases with increasing percentage reduction, but apparently he studied only the surface material, which Gensamer and Meh17 found to be somewhat differently oriented from the material in the inside of the sheet. McLachlan and Davey10 found that the deviation also decreases with increasing percentage of total reduction for the material in the interior of the sheet and is independent of the percentage of reduction per pass. The deviation about the cross direction as an axis (the direction in the

Jan 1, 1937

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By N. A. Gjostein

The real and apparent dependence of the surface self-diffusion coefficient, Ds, of gold on crystallo-graphic orientation has been investigated by isolated scratch smoothing and grain boundary grooving experiments. No systematic variation of Ds with orientation was found along the [100] zone. In view of the experimental scatter in these results, however, only aniso-tropy ratios, p, greater than -1.3 would be detectable. Anomalously low values of Ds were found on the [0ll] and [110] zones when the diffusion direction lies along (the scratch or grain boundary groove is perpendicular to) these zones. By comparing these results with a previous y plot study of gold, it is hypothesized that this is not an intrinsic diffusivity effect, but rather it results from a decreased driving force for mass transfer at orientations where the y-plot curvature is negative and appreciable in magnitude relative to y. The characteristics of this type of anisotropy do not appear sEVERAL investigations1-7 have dealt with the anisotropy of the surface self-diffusion coefficient, Ds, of metals as measured by the decay of single or multiple to be in agreement with the hypothesis of fast diffusion along ledges in the surface structure. In certain cases the Fourier method of determining Ds, described in Paper I of this series9 was compared with the second moment analysis in order to determine whether or not the method of analysis affects the anisotropy ratio. While the type of analysis does influence the magnitude of the anisotropy ratio, this effect is not associated with the shape of the profile, but rather is connected with the iterative volume diffusion correction used in conjunction with the second moment analysis. It is further demonstrated that the volume diffusion correction can be too large by either method when the y-plot curvature effect is large. Certain orientations exhibit an unusual temperature dependence of Ds ; this is discussed in terms of the y-plot curvature effect and/or the influence of impurities on Ds . scratches in the surface. Depending on the system investigated, both large1"3'6'7 and small4'5 anisotropies in Ds have been found. Although adsorbed impurities undoubtedly play an important role in determining the magnitude of the anisotropy,8 there are other factors that can give rise to an apparent anisotropy in Ds, thus obscuring the true nature of an intrinsic anisotropy in

Jan 1, 1968

The following is an incomplete list of members and guests who called at Institute headquarters during the period Sept. 10, 19188 to Oct. 10, 1918. Thomas J. Adams, Rahway, N. J. A. N. Mackay, London, England. Henry M. Ami, Washington, D. C. A. W. MacNichol, San Francisco, Cal. Chester Atkinson, Peru, South America. Ernest Marquardt, Casper, Wyo. Bennett R. Bates, Berkeley, Cal. Lieut. S. A. Mewhirter, Denver, Colo. Robert S. Botsford, Petrograd, Russia. William A. Nelson, Nashville, Tenn. Juan Felix Brandes, Santa Barbara, Cal. Robert W. Olinger, Bahia, Brazil, So. G. A. Collins, Seattle, Wash. Amer. C. V. Corless, Coniston, Ont., Canada. G. Preumont, La Paz, Bolivia, So. Amer. F. T. Eddingfield, Washington, D. C. William H. Rettie, Yonkers, N. Y. C. Mason Farnham, Barre Plains, Mass. . Julius Segall, Minneapolis, Minn. F. N. Flynn, Trail, B. C., Canada. Robert Y. Seip, Franklin, N. J. Duncan D. Forbes, Humboldt, Ariz. H. M. Schleicher, Boston, Mass. Alexandre Gouvy, Paris, France. Chester Steinem, Ft. Monroe, Va. Henry G. Granger, Cartagena, Colombia, A. L. Sweetser, Pittsburgh, Pa. So. Amer. . H: E. Treichler, Creighton Mine, Ont., E. Harms, El Paso, Tex. Canada. Alfred G. Heggem, Tulsa, Okla. Frank A. W. Tullock, Yumbo, Colombia, H. B. Henegar, Mascot Tenn. So. Amer. A. M. Kivari, Denver, Edward I. Williams, Ft. Monroe, Va. T. M. Kniffin, Brookline, Mass. Alfred W. G. Wilson, Ottawa, Canada. Charles Lehman, London, England. Donald H. McLaughlin, Camp Meade,Md. C. E. Addams, who recently resigned as general manager for the Arizona Hercules Copper Co., has leased the Ray silver-lead property three miles from Ray, Ariz. Bennett R. Bates has resigned his position as general superintendent of the Cubo Mining & Milling Co., in order that he may take the examination for an officer of engineers.

Jan 11, 1918

* Kennecott Copper Corp. gets Charles R. Cox as president on Jan. 1. Mr. Cox is resigning his position as president of Carnegie-Illinois to take the new post with Kennecott, left vacant by the death of Mr. Stannard in September. •The ECA signed a contract in December to advance X3,600,000 to Newmont Mining Corp. to aid development of lead and zinc mines in French Morocco. The funds are to be repaid in lead and zinc for the United States' stockpile over a period of seven years. The mines are owned by the Societe des Mines de Zellidja, with which organization Newmont is associated. • Under the direction of John M. Brooks, Jr., general manager, the Matahambra mine in Cuba, will probably produce sufficient tonnage to make 4 million lb of copper per month during 1950. The grade is presently running between 7 and 10 pet. •S. H. Ash reports that the fatality rate per million-man-hr for the anthracite industry for 1949, through November, is 0.78. This is 15 pct better than that achieved during 1948, which was the lowest fatal injury rate in coal mining history. The first full year on record without a major disaster was recorded in 1949 (p. 34). •The Atomic Energy Commission has authorized the production of 200 lb of uranium metal for use under AEC license in non-Commission research projects. •A national survey of projected 1950 purchases of new machine tools, machine tool accessories, materials handling equipment, etc., just completed by the American Society of Tool Engineers reveals that, of the companies reporting, 80 pct state that they plan to buy either more equipment or the same amount as in 1948. • Armour Research Foundation is conducting investigations for the use of clay and shale deposits to make lightweight aggregates. The material is heated until it expands and forms material suitable for mixing with cement which it is hoped will be lighter, stronger, have better insulating qualities and will lower the cost of concrete. •In the first six months of 1949 the bituminous coal miners' average hourly earnings were $1.94 -as compared with X1.392_ national average for all manufacturing. Average annual earnings of full-time employees in the bituminous coal mines in 1948 were $3387 as compared with $2809 for all industry. •LaSalle Business Bulletin reports: "year ends on a rising trend in industry and trade ... nearly record-breaking demand from almost all sources keeps business high... most indicators but little below postwar peak... forces keeping activity high arestill powerful--changes in general business conditions likely to be slow and moderate." •Office of Internal Trade of the Commerce Department requests that technical data significant to the national security which is to be sent outside of the United States be submitted to it for an official opinion on the desirability of transmitting such information. This voluntary compliance program is part of our national security control. • Blast furnace slag reduced to 12 to 16 mesh is being used for sanding track at the Mont Coal mines of Armco. The slag replaces silica sand which caused silicosis. It has proved so effective and cheap that tests are being made to use the slag for rock dusting.

Jan 1, 1950

By F. Weinberg, L. MacAulay

DAVIS,' in an investigation of solute redistribution along molten rods of dilute silver in tin, concluded that at horizontal temperature gradients below approximately 5°C per cm very little convective mixing takes place. Cole and winegard2 observed temperature oscillations in horizontal melts of tin, with temperature gradients of several deg per cm. They associated the temperature oscillations with the presence of convective flow in the melt. At temperature gradients less than 1°C per cm they did not detect convective flow. In the present work, direct measurements of con-vective flow in liquid tin have been made using a radioactive tracer technique. The results indicate that extensive convective flow occurs at temperature gradients below those previously reported. The apparatus used to determine the extent of con-vective flow is shown in Fig. 1. The graphite boat Fig. l(a), has two rectangular channels both of which contain molten tin. Radioactive Ag110 in the form of Sn-0.2 pct Ag alloy was introduced at the end of one channel, by rotating the cylinder shown. A series of fixed thermocouples were positioned along the center of the second channel to determine the temperature gradient. It was assumed that the two channels had identical temperature distributions. The graphite boat was inserted into a vycor tube which was surrounded by a multiple winding tube furnace as shown in Fig. l(b). The tin was melted in an argon atmosphere. The distribution of Ag110, as a function of position along the boat at a given time after introduction of the ~g"', was determined with the

Jan 1, 1970

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By B. A. Wilcox, A. H. Clauer

DURING the course of an investigation on the high-temperature creep behavior of TD Nickel* (Ni + 2) vol pct ThO2), it was observed that the creep fractures were similar in appearance to low-temperature ductile fibrous fractures and creep ruptures by cavitation. Microfractographs of fibrous ruptures are typically characterized by a dimpled appearance, with second-phase particles frequently found near the bottom of the dimples.'-4 These somewhat resemble creep ruptures by cavitation, in that fracture occurs by void formation, with the subsequent growth and final merging of the voids to form a complete fracture.' It is the purpose of this communication to describe the creep fracture of TD nickel and suggest a mechanism for the rupturing process. The discussion is relevant to material crept to fracture in vacuo at a constant stress of 18,000 psi, over the temperature range 900" to ll00°C. The material used in this investigation was 1/2-in.-diam bar stock supplied by Du Pont, contain- ing 2.3 vol pct Tho2. The final fabrication treatment consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fibered structure with a transverse grain size of -1 µ and a longitudinal grain size of 10 to 15 µ. Selected-area diffraction indicated that the fiber axis was parallel to (00l), in agreement with the results of Inman et a1.6 The thoria particle size varied from 80 to 1000Å, with an average size of 400Å, and the mean particle spacing was about 1200Å. The remarkable structural stability7 was confirmed by annealing for 6 hr at 1300°C (about ' 0.9 the absolute melting point). Transmission electron microscopy revealed that the only structural change was a slight decrease in dislocation density. Furthermore, recrystallization or grain growth during creep has not been observed. All specimens were annealed in vacuo at 1300°C for 3 hr prior to creep testing. The following times to rupture were obtained for vacuum creep tests at a constant stress of 18,000 psi: 900°C, 854 hr; 930°C,

Jan 1, 1965

The Atlanta Mine is located in east central Nevada, in Lincoln County, 116 km (72 miles) south of Ely and 80 km (50 miles) northeast of the old mining town of Pioche. From this famous district, high-grade copper ore was mined and shipped to a smelter in Wales in the 1850s; an early day lead blast furnace was also in operation. The Standard Slag Company began operations in May 1975 on the well known Atlanta Mine, which was operated by Roy Hardy in the 1930s. The mill is currently processing 450 mtpd (500 stpd) of gold-silver bearing ore. Mining by open pit is in a brecciated zone occurring between limestone-dolomites on the foot wall and tertiary rhyolites on the hanging wall. The quartz breccia is considered among the most abrasive in the world - shovel teeth must be replaced every week. Stripping ratio is 3.9 to 1.0. Because of the hard abrasive ore, the crushing plant consists of four units: two jaw crushers in series, one Hydrocone, and one Gyradisc. Mine feed to the primary crusher is limited to 610 mm (24 in.) in size. The remaining crushers work in closed circuit with screens to produce a mill feed of 6 to 13 mm (0.25 and 0.50 in.). Hardness of the ore is demonstrated by the fact that the reversible liners of the primary jaw crusher had to be replaced in early 1978 after handling only 39,000 mt (44,000 st) at a cost of $0.095 per mt ($0.086 per st). Another example of the extreme abrasiveness of the breccia ore was the total cost per ton in 1977 for all wear parts in the comminution circuit, including screens and grinding media. This amounted to $2.84 per mt ($2.58 per st). The Atlanta grinding plant consists of three ball mills to grind the 7 mm (1 /4 in.) crushing plant product to 85 to 90% minus 150 microns (100 mesh). Feed rate to the primary Tricone mill is determined by maintaining a cyclone overflow at 28 to 38% solids, which controls the grind mentioned above. A mixture of 90 and 65 mm (3.5 and 2.5 in. ) balls are charged to this primary mill. Both the secondary mills are charged with 50 mm (2 in ) balls. Total ball consumption is 2 kg per mt (4 lb per st). All three ball mills use rubber liners. Primary mill cyclone underflows are fed to the secondary mills close circuited with the same cyclones.

Jan 1, 1981

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at subcritical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.1 Westgren, Phragmén and Negresco2 identified the following carbides in chromium steels: [Cementite Fe3C (containing up to about 15 per cent Cr) Trigonal carbide Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide Cr4C (or Cr23C3) (containing up to about 25 per cent Fe) Orthorhombic carbide . Cr3C2 (containing only a few per cent Fe)] The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus.4 By means of dilatometric and microscopic studies, sections of the diagram were established. This diagram showed the presence of the special carbide Cr7Ca in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in r per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7Ca occurs in chromium steels containing more than about 1 per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. EXPERIMENTAL PROCEDURE The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into 1-in. round bars, and all heat-treatments were conducted on specimens of this section .size. Sections of the bar stock 8 in. long were hardened in air, oil or water depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after auenchine. The quenched bars were cut into

Jan 1, 1942

THE only asbestos mine in the Middle East is on the Island of Cyprus, high in the Trodos Mountain village of Amiandos. The mine is owned by the Tunnel Asbestos Cement Co. Annual output is some 18.000 tons of short fibre in the 4-T. 4-Z, and 5-R grades.

Jan 9, 1953

By J. J. Gilman

THEORIES of fracture in metals have been based primarily on the dependence of fracture strength on grain size. This dependence was first observed by Masing and Polanyi.l These workers, as well as 0rowan12 and Davidenkov and Wittman,' thought the grain size could be equated with the crack size in the Griffith condition for crack propagation.4 In this way they could account for the observed proportionality between fracture stress and the reciprocal square root of the grain size. The chief results of recent investigations of the fracture strength of polycrystals are summarized in Fig. 1. Low for iron,5 Petch for iron,' Greenwood and Quarrel for zinc, Petch and Zein for zinc,' and Hauser, Landon, and Dorn for magnesium'' have all found that the fracture stress of a polycrystal is proportional to the reciprocal square root of the grain size. Also, they find that, for large grain sizes, the fracture stress lies near the extrapolation of the yield-stress curve determined at small grain sizes; where measurable plastic strain precedes fracture. Low9 has gone a step further and shown that, in Range 1, the fracture stress in tension is almost identical to the yield stress in compression for a given grain size. Homes and Gouzou, 10 and Low also have shown that, in Range 2 of Fig. 1, microcracks form when the yield stress is reached, but they do not cause failure until the stress reaches a much higher value. The fact that yielding always precedes fracture suggests that fracture is induced by plastic flow. A mechanism by which this might occur was first proposed by Zener.11 He pointed out that blocked dislocations would cause stress concentrations which might cause fracture. The blocking would be caused by grain boundaries. This idea has been developed by Eshelby, Frank, and Nabarro,12 by Koehler,13 and by Stroh.14 By means of etchpits blocked dislocations have been observed in brass by Jacquet,15 in zinc by Gilman,16 and in lithium fluoride by Gilman and johnston. The blocked-dislocation theory and the experiments that bear on it have been summarized by Mott.18 One of the strong points of the blocked-dislocation theory is that it can explain the grain-size dependence of the fracture stress in a natural way. However, Low9 has pointed out that the theory is not satisfying when it is considered quantitatively. Gilman10 also has criticized the theory and presented an alternative interpretation of the relation between fracture stress and grain size. Since the blocked-dislocation theory is not the only theory that can explain in the grain-size effect, it is necessary to find other evidence either to support or deny it. In this investigation the following points were studied: 1) If blocked dislocations normally cause fracture, then the fracture stress ought to be very high in the absence of plastic glide. Is it? 2) If dislocations must be blocked in order for metals to fracture, then certain types of grain

Jan 1, 1959

By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.' This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT's 'connected in an averaging 'On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--' * *H - >^> - ' ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By R. S. Sandhu, L. E. Baker, W. Y. Shieh

The finite element method of analysis was introduced by Clough.1 Within a short period, it has developed into a powerful solution technique in structural and continuum mechanics. It has been used to solve boundary value problems in two and three-dimensional elasticity.2-5 Anisotropy and heterogeneity of materials were allowed for at the earliest stages. 1,4 Its application has been extended to allow for cracks,5 creep and viscoelasticity, 6,7 incremental construction,6-8 nonlinear elasticity3,9 effect of joints in rock,10 and to materials with different behavior in tension and compression.7 Because of its versatility, the finite element method has found increasing application in the field of rock mechanics. In fact, several of the more significant developments have been motivated by problems in this field. Elasto-plastic material behavior based on the incremental or rate-type theory of plasticity rather than the deformation theory was considered by Reyes and Deere11 A material law based on a generalization 12 of the Mohr-Coulomb criterion was used. In this chapter, the formulation of material laws developed by Reyes and Deere 11 is used. An efficient analysis procedure, incorporating recent developments in finite element analysis, is developed for plane-strain conditions. To demonstrate its effectiveness, the procedure is applied to three cases, one for which an exact solution is available, another for which field observations had been made, and a third one for which a parallel study was made, using an accepted limit-equilibrium method.

Jan 1, 1970

By Peter F. Weiss

INTRODUCTION Austro-American Magnesite Co. of Radenthein, Carinthia, Austria, is a wholly owned subsidiary of General Refractories Company, Bala Cynwyd, USA, and has been incorporated since 1908. The raw material basis is the magnesite mine on Millstatt Alp, located in the mountains near Radenthein at an altitude of 1500 m above sea level. The mined crude magnesite is crushed in a surface crushing plant to minus 35 mm and consequently hauled to the processing plant in the valley by means of a cable conveyor of 7.5 km length. The annual production of 350,000 mt is accomplished with 20 supervisors and 122 workers (of those 60 are in the mine). The labor requirement for block caving is 0.2 man hr/mt, corresponding to an output of 40 mt/man/ shift. GEOLOGY The rock in this area mainly consists of crystalline type schist. There are mostly coarse crystalline garnet mica schists with varying mineral concentrations, and to a lesser degree, some deposits of amphibolite and marble. This petrographically rather homogeneous rock is divided into numerous different tectonic units (covers and scales). The magnesite deposit itself is a foreign body that also has been tectonically inserted. The ore body has a length of 600 m, is 450 m deep, and has a thickness of 60 m on average, varying substantially however, The contact with the accessory rock is very precise. The deposit 1 = ore body, 2 = previous open pit, 3 = caved in area, 4 = block under excavation, 5 = land slide consists of coarse crystalline magnesite in excess of 90 per cent. The few impurities consist of dolomite and talc. The lower part of the deposit is inclined parallel with the schists at approx. 40 degrees. In profile it can be seen, however, that the upper part of the deposit has been tilted over. This is a result of a post-glacial land slide reaching from the bottom of the valley at 1400 m above sea level to the peak of the mountain at 2100 m above sea level. Due to this land slide, with horizontal movements of up to 100 meters, as well as older tectonic events, the rock was crushed to a vast extent. Through mining, the land slide was reactivated; about 40 million cubic meters of rock slowly flow downhill almost like a plasticized mass. Near the surface, the rock is completely crushed and resembles a glacier rupture zone. This renders the originally impermeable rock completely water permeable so that practically all of the annual quantity of 1000 to 1100 mm of precipitation permeates the rock and flows down into the mine. The carbonate rock turns into the preferred aquifer. From 1700 to 2600 cubic meters of water have to be pumped from the mine daily. On one hand, additional problems are caused by the water in the mine, on the other hand we have learned to make use of the down- hill pressure forces to improve the crushing process during block caving. The boundary of the downhill shearing zone moves downward as mining goes deeper.

Jan 1, 1981