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By A. J. McEvily, R. C. Boettner, C. Laird

The processes leading to fatigue failure in the low-cycle range were studied to obtain an understanding of the basis of Coffin's law. Particular attention was paid to the manner of mack nucleation and to the determination of the portion of the total lifetime spent in crack propagation. It was observed that cracks are nucleated at surface notches meated during reversed plastic deformation, Principally at grain boundaries, and that crack growth occupies greater than 75 pct of the fatigue life. When inclusions are present, they are often the primary sites of crack initiation. From consideration of the incremental distances advanced by a crack in each cycle and of the lifetimes of different materials, it appears that the universality of Coffin's law arises from the similarity of crack-tip strain for a given applied strain amplitude, irrespecti7:e of material. STUDIES of low-cycle fatigue have been particularly rewarding in that a simple correlation between fatigue lifetime and plastic-strain range has been shown to exist. This empirical relationship takes the forml,2 Nner=C [1] where N is the number of cycles to failure, Er is the plastic-strain range defined as the total plastic strain per cycle (the sum of the tensile plastic strain plus the compressive plastic strain), n, the exponent, is a constant independent of the material to a first-order approximation and often has a value of about 0.5, and C is a constant which for a number of ductile and metallurgically stable materials is approximately 0.65 for fully reversed strain.3 This relationship has been shown to be valid for a wide variety of metals and alloys and is often referred to as Coffin's law. However, it is yet not clear why so many different metals and alloys exhibit the same over-all behavior in the low-cycle range. Less is known about the mechanisms of fatigue failure in the low-cycle range than in the high-cycle range, but it is expected that the processes would have much in common. For example, an important characteristic common to both high-and low-cycle ranges is that fatigue crack propagation can occupy a considerable portion of the total lifetime. This has been shown by Laird and smith4 by a count of the number of ripples present on the fracture surface of copper specimens, each ripple corresponding to one cycle of load. On the other hand, some marked differences have been noted. For example, in copper,5 nickel, and aluminum4 there is a greater tendency for grain boundary cracking to occur as the strain amplitude is increased. The purpose of the present work was to study further the processes leading to fatigue failure in the low-cycle range and to obtain an understanding of the basis for the validity of Coffin's law. Particular attention has been paid to the manner of crack initiation and to the determination of the portion of total lifetime spent in crack propagation. MATERIALS A number of metals and alloys were tested, although more attention was focused on a particular few, once general trends had become apparent. Alloys were selected so as to investigate the effects of crystal structure, number of phases, stacking-fault energy, and impurity content. The materials in this grouping were: high-purity copper OFHC copper 1100 aluminum (commercially pure) 70-30 brass (Cu-30 wt pct Zn)

Jan 1, 1965

By A. A. Dor

Recent developments in the design of concentration plants have reflected the increased recognition that has been given to the economic and metallurgical advantages of autogenous grinding. This has manifested itself in the increasing adoption of primary auto genous grinding in iron ore 'beneficiation plants in North America. Table 1 lists eleven major iron ore beneficiation plants which have either been put in operation since 1961 or are under construction at present. Seven out of these eleven plants have adopted primary autogenous grinding. Four of them have coarse grinding mills (8 to 14 mesh) and three have fine grinding primary circuits (48 to 65 mesh). Their nominal capacity totals 26. 2 million ltpy of concentrates or pellets, representing very nearly 75% of the aggregate capacity 135. 3 million ltpy) of the eleven concentrators listed. For a long time there was a tendency to consider that primary autogenous grinding was only applicable to suitable coarse grained ores, However, extensive testing of a very wide variety of ores, and actual operating performance in several commercial plants, seem to have established beyond reasonable doubt, that the majority of mineral ores which the beneficiation engineer may be called upon to process can be ground autogenously. The basis for the selection of autogenous or conventional grinding mills, becomes principally economic and depends on the liberation characteristics of the ores under consideration and their relative hardness and grindability.

Jan 1, 1965

By E. J. Karges

The use of pulverized coal for generating power and performing industrial processes has made an important contribution to our industrial economy during the past half century. Actually, the burning of coal in powdered form is a subject that has held the attention of engineers for a century or longer. Its widespread use, however, is comparatively recent, As early as 1866 patents were granted to Messrs. Whelpley and Storer for a method of feeding pulverized coal into a furnace as an auxiliary to the grate fuel. In the many tests made during the subsequent years with various kinds of apparatus, the experimenters were handicapped in not getting the coal fine enough to obtain complete combustion and to prevent excessive formation of slag.

Jan 1, 1965

This paper comprises a description of on-stream analysis instrumentation, including sample handling, X-ray optics and data processing. It also includes a discussion of some typical applications of an on-stream analyzer as related to the mineral processing industry. Introduction T WO automatic X-ray spectrometers have been developed for the simultaneous analysis of as many as six elements in a given sample. These instruments, namely the On-Stream Analyzer and the new Vacuum Simultaneous Spectrometer, have been designed specifically for process control in industry where large numbers of static samples or a number of flowing sample streams must be analyzed continuously with both speed and accuracy. This paper is concerned particularly with the application of these instruments for the continuous analysis of dynamic samples. The Instruments The On-Stream Analyzer and the Vacuum Simultaneous Spectrometer are intended to serve industry by offering two basic approaches to the problem of continuous sampling of flowing sample streams. The On-stream Analyzer (Figure 1) is designed for the completely automatic and unattended analysis of flowing sample streams in a programmed cycle of operation.

Jan 1, 1965

By W. M. Robertson

The kinetics of grain boundary groove formation on copper surfaces immersed in liquid lead have been studied over the temperature range of 400° to 900°C. The groove widths were Proportional to the cube root of the annealing time, indicating that the diffusion of copper through the saturated liquid-lead solution is the mechanism by which grooves form. The rate constant for the process can be calculated by a theory due to Mullins. Using published data for the solubility of copper in liquid lead, for the interfacial energy of the solid copper-liquid lead interface, and for the diffusion coefficient of copper in liquid lead, the calculated rate constants almost exactly reproduce the measured values over the entire temperature range. The decay of scratches placed on copper surfaces has also been studied. The rate constant for scratch decay agrees with that for grain boundary groove growth, though scratch decay is sensitive to convection currents in the liquid. The interaction of solid and liquid metals has been studied extensively and has been found to be rather complex. Many of the studies have been complicated by a host of competing effects, including temperature gradients, concentration gradients, the formation of one or more intermetallic phases, natural or forced convection, and the presence in both the solid and liquid of considerable amounts of impurities and alloying elements. Recently theories have been developed of changes in surface profiles driven by capillary forces,' which allow the interaction of the solid and liquid to be analyzed quite directly. The present paper reports a study of the formation of grain boundary grooves on pure copper immersed in liquid lead, which allows the theory to be checked quantitatively. The Cu-Pb equilibrium diagram is quite simple: there are no intermetallic compounds, copper is just slightly soluble in liquid lead, and lead is almost completely insoluble in solid copper.2 The Cu-Pb system has been studied extensively,3-9 and all of the quantities—interfacial energy, diffusion coefficients, and equilibrium solubilities-necessary to calculate the rate of groove growth by a volume-diffusion mechanism are known. The kinetics of grain boundary grooving and scratch smoothing have been studied on the noble metals and the iron group metals in a reducing atmosphere or in vacuum.10 The main interest of these studies has been the determination of surface-diffusion coefficients at metal-gas interfaces using the theories developed by Mullins.1 The present paper uses similar methods for the study of diffusion processes at the interface between two condensed phases. There has been one previous study" of the kinetics of groove growth in a solid-liquid system, which, however, was troubled by the fact that neither interface energies nor diffusion coefficients were known in the Ni-S system studied. THEORY The theory of grain boundary groove growth has been developed by Mullins for the cases of volume diffusion," surface diffusion," and a combination of the two processes.14 He has also analyzed the kinetics of the flattening of a scratched surface by these processes.l5,l6 Several assumptions and approximations were used in the derivations of the surface profile shapes. The applicability of these assumptions and approximations to the present system will be considered in the discussion. At the intersection of a grain boundary with an initially flat interface the equilibrium between the interfacial energy and the grain boundary energy establishes an equilibrium groove angle. This induces curvatures in the interface. The chemical potential of material at a curved interface is higher than at a flat interface, so that material moves away from the region of the grain boundary. Mullins' calculations indicated that the groove profile would be similar to that shown schematically in Fig. 1. Small humps form above the level of the original flat surface. For a volume-diffusion mechanism the separation, w, of these humps at a time, t, is given by and where co is the equilibrium concentration of the solid in the liquid, y, the solid-liquid interfacial free energy, O the volume occupied by a solute atom in the liquid, D the diffusion coefficient of the solid in the liquid, and kT has its usual meaning. For a surface-diffusion mechanism the groove width is proportional to the fourth root of the time. For grooves forming by a combined surface and volume-diffusion mechanism the exponent of the

Jan 1, 1965

By Albert W. Deurbrouck

Twelve samples from six Barbour County coal beds were analyzed for this report. The samples collected were generally high sulfur content coals, frequently exceeding 3 percent in the raw-coal sample. Many of them could not be upgraded to acceptable metallurgical standards even by rigorous preparation procedures. The production of coal in the county in 1963 amounted to almost 3 million tons of which 44 percent was mechanically cleaned.

Jan 1, 1965

By D D. Deacon

A brief description is given of the requirements which No. 4 Shaft has been designed to meet and of the methods by which two-stage winding of rock has been accommodated in a single shaft sunk to a depth of 7,421 ft. This is followed by a consideration of the factors which led to the decision to sink the shaft as rapidly as possible. Introduction T HE No. 4 Shaft of Hartebeest-fontein Gold Mining Company, Ltd., has been sited to serve the deep southern area of the mine, some 1,500 claims in extent, between the elevations of 6,250 and 7,300 ft. below surface. From this area, some two-thirds of the mine production will ultimately be obtained. Above the 6,-250-ft. elevation, an existing shaft hoisting system, situated adjacent to the reduction plant, is of adequate capacity to cater for all ore hoisted to surface for milling. No. 4 Shaft will therefore be required to provide downcast ventilation of 1,000,000 c.f.m., together with surface hoisting facilities for men, material and development rock and underground hoisting

Jan 1, 1965

By F. Wald, A. J. Rosenberg

The general features of the constitution of the B-Pt system were determined using standard rnetal-lograph~c, thermoanalytic, and X-ray diffraction techniques. Three compound were found. Two of these, Pt3B and Pt,B, are formed by peritectic reactions at 523° and 890°C, respectively. The third, Pt3B,, is congruently melting with a flat maximum at 940°C but decomposes eutectoidally in to Pt,B ant1 boron nt - 600° to 650°C. THE low-temperature allomorph of boron (red, simple rhombohedra1 a boron) is of scientific and technological interest as an elemental semiconductor.' However, the studies of this material have been hampered by its reported instability above 1200"~ which precludes crystal growth from the melt (mp - 2200°C). Crystallization from platinum solutions has been suggested as an alternative crystal-growth technique, but has met with only limited success.' The technique depends upon the existence of a significant difference between the eutectic temperature and the transformation temperature of boron. In order to clarify the conditions for further crystal-growth experiments, we found it desirable to redetermine the main features of the B-Pt phase diagram since previous reports on the system1'5'6'7 are in marked disagreement. EXPERIMENTAL The experimental methods used were thermal analysis, metallography, X-ray analysis, and, to a lesser extent, measurements of microhardness. Most of the alloys were prepared from spectrograph-ically standardized boron obtained from Johnson-Matthey &Co., Ltd. (212 ppm impurities, exclusive of carbon and oxygen) and platinum powder obtained from F. Bishop & Co. (200 ppm impurities, mainly of other platinum group metals). Some alloys were also prepared with very high-purity, float-zone refined boron (99.9999 pct obtained from "Wacker Chemie" and extrahigh-purity platinum (99.999 pct) obtained from Johnson-Matthey & Co., Ltd. The reported results did not depend on the choices of these starting materials. Five-gram alloy specimens containing 10, 20, 25, 27.5, 30, 33.3, 34, 35, 37, 37.5, 38, 39, 40, 41, 42, 43, 45, 50, 55, 60, 70, and 80 at. pct B were made by melting the elements together in boron nitride crucibles using rf heating of a graphite susceptor, either in vacuum or under high-purity argon. All alloys were heated to at least 1800°C for -5 to 15 min. Most of the alloys did not wet the crucibles when the latter were outgassed by preheating under vacuum. In any event, no weight loss was detected after melting, and the nominal composition was assumed for all specimens. Thermal analysis on 2.5-g samples were carried out in boron-nitride crucibles under a vacuum of 5 x X torr. The apparatus was heated in a "Kan-thal A 1" wound furnace, which limited the maximum temperature to about 1100°C. The output of the indicator thermocouple was fed to a dc recorder with a 1-mv full-scale span and an adjustable zero. The apparatus was calibrated repeatedly, using the freezing points of high-purity aluminum, silver, and gold. The results justified the use of the NBS voltage vs temperature tables for Pt/Pt 10 pct Rh thermocouples. All thermal analyses were run at least twice and both the heating and cooling effects were recorded. Most of the alloys had a very strong tendency to supercool. However, the use of mechanical vibration permitted reproducibility within *5°C for all alloys, except in the region around 40 at. pct B. Only the cooling effects are plotted in Fig. 2, since they appear to be more reliable. For metallography, the alloys were cut with a diamond cutting wheel, cast in a polymethacrylate resin, ground and polished with diamond paste, and etched with dilute aqua regia, a common etch for platinum alloys. Both copper and molybdenum radiation were employed to obtain X-ray diffraction data using Debye-Scherrer cameras and a "Norelco" diffractometer Diffractometry with high scanning speeds (1 deg per min) using nickel filtered CuK, radiation was used to identify the main regions of the diagram. However, molybdenum radiation was used for the detection of boron, since the latter showed very strong absorption and fluorescence effects with CuK, radiation. RESULTS AND DISCUSSION Three intermediate compounds, corresponding to the compositions Pt3B, Pt2B, and Pt3B2, were found in the system. Fig. 1 reproduces their X-ray diffraction spectra, together with those of pure boron and pure platinum. As can be seen from the thermal-analysis data in Fig. 2, Pt3B and Pt2B are formed by

Jan 1, 1965

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By C Carbonneau

In order to successfully produce columbium pyrochlore concentrates, St. Lawrence Columbium and Metals Corporation had to face two principal problems met in several new operations but possibly made more acute than usual owing to the newness of the project. 1.-The ore is particularly complex, as it is made up of an elaborate intermingling of carbonates and discontinuous ultra-alkaline rock bodies of various ages and types in which no less than seventy mineral have been re-ported. Obvious petrographic or structural controls are lacking. Ore boundaries have to be defined on the basis of assay results and the determination of several minerals which occur in trace amounts. 2.-The pyrochlore concentrates produced had to com-ply with a set of stringent specifications. This fact, combined with the low Cb205 content of the ore, necessitated the use of a beneficiation process that would have to operate at a concentration ratio greater than 100:1. A brief description of the mill circuit is given. Mill stability was obtained through extensive mineralogical study of the mill feed coupled with close geological and engineering control of the mining operations.

Jan 1, 1965

By J. Richter, D. Schulze

J. Richter and D. Schulze (Deutschen Akademie der Wissenschafte zu Berlin)—Introduction. In a recent paper R. G. Garlick and H. B. Probst reported on experimental results of investigations of room-temperature slip in zone-melted tungsten single crystals.17 In the paper it was pointed out that slip lines could be detected with an optical microscope only after about 10 pet plastic strain of the crystal. In our investigations we could observe slip lines in tungsten single crystals of defined orientations already with an elongation of 0.02 to 0.03 pet.18"9 Experimental Technique and Results. The tungsten single crystals were produced from 4 to 5 mm sintered rods* as starting material by electron- beam zone melting. With single-zone-pass melting a speed of 0.5 mm per min was used, while three-pass melting could be handled at a speed of 3 mm per min. Crystal axis orientations were located in the shaded area of the stereographic triangle, see Fig. 6. Orientation 1 is located at about 18 deg and orientation 2 at about 5 deg on the great circle from [011] to [ill]. This corresponds approximately to the orientations P and M referred to by Garlick and Probst. Our single crystals had a length of about 70 mm and were profiled solely by electrolytic means, leaving grip ends at both ends of the crystals. Between the latter, a cylindrical crystal of 45 to 50 mm length and about 2.4 mm diam was obtained. The crystals were deformed at room temperature in a commercial tensile-testing machine to obtain a strain of 0.02 to 5 pet. The average strain rate e = eP/t for all tensile tests amounted to approximately 10 -6 to 10-5 per sec, with ep representing plastic strain and t the duration of applied stress. In Fig. 7 a crystal is shown elongated by 0.03 pet. The picture was obtained by means of an optical microscope. Figs. 8 and 9 give electron-microscopic pictures of slip lines of crystals elongated by 0.07 and 1.1 pet, respectively. For crystals with the orientation 1, see Fig. 6, only the two main slip systems (101)[111] and (110)[111] were found. With the crystals of group 2 the two main slip systems are again evident, with

Jan 1, 1965

By P. C. Kapur

The kinetics of green pelletization in a laboratory balling drum have been studied, using pulverized limestone as a model system. The growth characteristics of green pellets were found to be extremely sensitive to the moisture content of the material. Empirical kinetic equations, which incorporate a function of specific surface of the pellets as the criterion for growth potential, have been found to describe growth in a nucleation region and in a ball growth region. The rate constants in the kinetic equations are strongly dependent on the moisture content of the material being pelletized. Size distributions of the halls at different stages of pelletizing are also discussed.

Jan 1, 1965

By J. E. Miller

Primary standard gas mixtures were developed for more accurate calibration of analytical instruments at the Bureau of Mines Helium Research Center and for calibration of analytical instruments used in the helium conservation program. A 10-kg-capacity balance is used to weigh a 4-kg metal cylinder filled to high pressure (1,800 psi maximum) with the component gases of the desired mixture. At 1,800 psi, a cylinder contains about 60 g of helium, or 420 g of nitrogen. An accuracy of ±0.05 mole-percent or better is claimed for each component in the mixtures.

Jan 1, 1965

By Delbert L. Keenon

The principal concepts of computer control and automation have been successfully applied in industries world-wide, The enthusiasm generated by the proponents of computer control, and the apparent mystery enveloping the techniques of computer control, have caused attention to be focused on this infant industry from all quarters. Consequently, the motivation to "computerize" may be the hope that computers will solve all economic problems. The truth remains that not only have there been monumental successes, but there have been some colossal failures. This paper will attempt to outline a generalized guide to computer control and present methods for avoiding some of the major pitfalls. Since the investment required for computer control systems has been drastically reduced in the past year, small operations will likely find that computerized process control is attractive in areas where it has never been considered before, The discussion presented here is intentionally non-technical and directed towards those who may soon find they have a possible application for a control computer. The primary purpose of computer control is to reduce expenditure and increase profits by improving the quality of product, increasing the efficiency of operation, reducing the materials and man hours required or a combination of these. Success or failure to reach the desired goal depends, to a large degree, on a well-planned approach. This includes recognizing a possible computer application, properly defining the job which is to be accomplished, evaluating computer systems, selecting a capable manufacturer, and following through with sound systems engineering and programming.

Jan 1, 1965

By W J. Riva

This paper reviews the coal mining operations of The Canmore Mines, Limited, at Canmore, Alberta, paying particular attention to the use of this coal by the metallurgical and chemical industries. The characteristics of the deposits are outlined, and the mining and processing methods used are discussed. Introduction M INING in the Cascade coal area of Alberta began form-ally in 1886 when the Canadian Anthracite Coal Company was granted its charter. Earlier operations had been confined to prospecting and family-type enterprises serving the market area within barging distance on the Bow river. From 1886 to 1964, seven mines were opened between Banff and Ribbon Creek; six of these have since been abandoned, leaving the B c 0 L. original tenant, under the name of The Canmore Mines, Limited, as the sole survivor. The town of Canmore, hub of the mining ventures, is located on the main line of the C.P.R. and on the Trans-Canada Highway, 67 rail miles west of Calgary and 57 4 miles east of Vancouver, as shown in Figure 1.

Jan 1, 1965

By William H. Lehr

In recent years, we have witnessed many innovations in the equipment used in handling bulk materials. Not too long ago, any sizeable stockpile of coal or iron ore was attended by one or more material handling bridges. More recently, large stockpiles have been built with mobile equipment of' the earth moving type with bulldozers and front end Loaders being utilized in reclaiming operations. The most recent stocking and reclaiming device is the rotary bucket wheel machine. The early bucket wheel machines built in the United States were developed for the strip mining of coal. We understand that the first American machine was built in the Midwest in 1944. This type of unit was developed in an effort to reduce the cost of removing overburden and to provide satisfactory spoil disposal. As the available coal reserves under shallow cover were exhausted, the cost of removing the deeper overburden with conventional equipment became too great for these operations to continue profitably. The first machine has now been followed by six or seven additional units, the largest of which can handle material at a rate of more than 7000 cubic yards per hour.

Jan 1, 1965

By P. S. Rudman

The allotropic volume changes of the ,metallic elements are reviezoed with the conclusion that in general atomic volume is conserved to better than 1 pct in such transformations. A table of the atomic volumes of the metallic elements is given and its use in considering the size factor in alloys is discussed. The importance of the concept of atomic-size factor, due to Hume-Rothery and coworkers,' is firmly established. Most attempts at quantitative formulations of this concept have employed the atomic radius (half some interatomic distance) as the measure of size and innumerable tables of such radii exist. This is probably, however, an unfortunate choice of parameter. Firstly, discussion in terms of interatomic distances requires a knowledge of the crystal structure. While this is known, except for a few cases, for the elemental structures, there are still many undetermined alloy structures. Secondly, except for the simpler structures, face-centered cubic (Al),* body-centered cubic (A2),* and hexagonal-close-packed (A3).* with ideal axial ratio, there is no unique in- teratomic distance, an m y decision must be made as to which distance, or which average of the distances, should be used. However, the most important point is that for metals the dominant bonding parameter can generally be expected to be atomic volume and not interatomic distance. This is perhaps most explicitly stated in the Wigner-Seitz cellular method.' In this approximation, cellular polyhedra of atomic volume v are replaced by spheres of radius Y,: 4/3 ?rs3 = v. That is, there is no reference to the interatomic distances. If atomic volume is in fact the dominant parameter, then in allotropic transformations we might expect to find atomic volume approximately conserved. For example, in the A1 ? A2 transformation we would thus have

Jan 1, 1965

By Dell P. Williams, Howard G. Nelson

The tensile behavior of magnesium single crystals at a temperature of 26º ± 2ºC was investigated at varying pressure levels from 760 to 8 X 10-8 tow. For crystals deformed at a constant linear strain rate of 0.061 min-1. there was no apparent effect of the vacuum environment down to 10-8 torr. However, from a vacuum of 10-5 torr down to the lowest pressure attained (8 x 10-8 tor,), the effect of the vacuum environment was to increase the strain at the end of the first linear (or easy-glide) stage and to decrease the slope of this stage; the magnitude of this effect was found to be dependent on pressure. The slope of the second linear stage was also decreased at the lower pressure levels; however, this effect appears to be caused primarity by the vacuum effect on the first linear stage. The magnitude of the vacuum-environmrnt effect was also found to be dependent upon strain rate. The reduction in flow stress at 5 x 10-8 torr, as compared to the stress in air, was obserced to be about 10 pct for a strain rate of 0.0250 min-' and 70 pct for a strain rate of 0.67 min-1. No systematic effect of pressure on the critical resolvled shear stress was observed. The data interpreted in terms of a modified form of Mott's work-hardening mechanism for hexagonal metals. It has long been known that surface conditions influence the mechanical behavior of materials. Roscoe 1 demonstrated the importance of surface conditions on mechanical behavior by testing cadmium crystals with oxide layers. He found that the "apparent" critical resolved shear stress for cadmium was increased approximately 2.5 times by the presence of an oxide layer 1000 atoms thick. The magnitude of this effect was dependent on film thickness with crystals having films less than 20 atoms thick still showing a definite increase. This observed strengthening could not be attributed to any strength of the oxide film because of 1) the thinness of the films and 2) an observed increase in the flow stress as deformation proceeded. Harper and cottrel12 obtained similar results on zinc crystals which had been etched and steamed to give artificially thick oxide films. However, in the course of this study, they also carefully examined the very early stages of plastic flow for zinc crystals which in one case had been electrolytically polished and in the other had been lightly etched to produce a thin film. They then found that the critical resolved shear stress for both surface treatments of the crystals was actually identical but that the etched crystal exhibited a much more rapid initial hardening rate. This had not been noted previously. This result indicated that, in fact, the film caused an increase in the stress for continuation of slip, rather than for the initiation of slip. Lipsett and King3 investigated the effect of evaporated gold films on the plastic behavior of cadmium single crystals. For large angles (=75 deg) between the specimen axis and the normal to the slip plane, they found that the stress-strain curve of the coated specimen always lies above that for a clean specimen. The shear strain at the end of the first linear stage was greater in clean specimens than in coated specimens and the slope of the second linear stage was

Jan 1, 1965

By A. W. Henderson

This investigation was performed to develop chlorination methods for extracting tungsten from scheelite and from an ore concentrate containing a mixture of scheelite and wolframite. On a laboratory scale with proper temperature control using elemental chlorine, over 90 percent extraction of tungsten is achieved. Carbon and sulfur dioxide were studied as reducing agents. The effects of salts such as calcium fluoride and sodium chloride were studied as additives to increase extraction and to reduce impurities in the volatile tungsten chloride product. Sodium chloride reacts with ferric chloride to form a nonvolatile double salt; whereas the chlorides and oxychlorides of tungsten are volatile and consequently condense free of iron. Separation of tungsten from molybdenum from an equal molar mixture was successful by fractionally distilling the oxygen-free chlorides and by selectively condensing the oxychlorides. Yields of 60 and 80 percent, respectively, were achieved for separating the less volatile tungsten chlorides containing less than 0.5 percent molybdenum.

Jan 1, 1965

By D. K. Atwood

Experiments resulted in a satisfactory laboratory method for restoring permeability to clay-containing cores damaged by fresh water. Clay contents of a number of field cores were measured, and permeabilities of plugs from these same cores were then deliberately reduced with fresh water. This damage is attributed to swollen and dispersed clays occupying the pore space. After damaging, a number of experiments were performed to meaJure the amount of damage and to establish some means by which permeability could be restored. The experiments included flooding the damaged cores with water-miscible fluids such as salt water, acetone, isopropyl alcohol and ethanol. Permeability was not successfully restored in these experiments. However, part of the damage was repaired by flooding with oil; when water was removed by distillation in the presence of immiscible fluids such as air or toluene, permeability was completely restored. This evidence suggested that swollen and dispersed clays could be collapsed to their original volume by strong interfacial and capillary forces. It was further postulated that the required forces could be generated by flooding the damaged cores with a solvent partially miscible with water. The flooding experiments were repeated using n-hex-an01 as the partially miscible solvent. Permeability was restored to five of six damaged cores and substantially increased in the sixth. A large fraction of the restored permeability was retained even after water saturation was raised to its original value with 12 per cent salt water. INTRODUCTION Sharp reductions in permeability often occur when relatively fresh water contacts clay-containing formations during drilling and workover operations. These permeability losses are caused by removing inorganic ions from the environment surrounding the clay, and consequent swelling and/or dispersion of clay minerals into the available pore space.' This phenomenon is generally termed clay damage, fresh-water damage, or simply formation damage; it causes large losses in current revenue by preventing oil wells from making their allowable production. Attempts to repair the damage and restore permeability by flowing salt water solutions or brines through clay-damaged cores containing montmorillonite have been unsuccessful.' This irreversibility is thought to result from formation of brush-heap, or edge-to-face, structures when the dispersed clay is flocculated. The brush-heap structures occupy much more space than the close packed domains present before damage.' One solution of the problem is to destroy the clay-water brush-heap and thus restore permeability. Because no satisfactory method existed for restoring permeability to clay-containing formations damaged by fresh water, the work described in this paper was under taken. The laboratory experiments generally consisted of deliberately damaging fresh cores containing clay and then attempting to repair this damage by various means. Results indicate that generating strong interfacial forces within the pore space of damaged cores collapses the clay brush-heap and restores permeability. These forces are most conveniently generated by flowing partially water-miscible solvents, such as n-hexanol, through a core. THEORY OF THE DAMAGE PROCESS The most common clay mineral groups known to cause permeability damage to formations are the mont-morillonites, kaolins, chlorites and illites. These clays are constructed of particles which can adsorb water on their surfaces and edges and, in the case of montmorillonite, between layers of the basic particle itself. This adsorption increases as water salinity decreases. At low salinities the particles disperse into the aqueous phase. When the clays present in the formation are kaolin, chlorite and illite, dispersion accounts completely for permeability damage to porous media. However, unlike the other clays, montmorillonite particles can imbibe water and adsorb ions between layers of sub-particles, or platelets. These platelets have net negative charges on their faces and are held together by exchangeable (or removable) cations such as Na and Ca decrease in ion concentration (salinity) in the fluid surrounding a particle causes migration of water into the clay layers and disperses the basic particle, while diffusion removes the original exchangeable ions from between the platelets. Once these ions are removed, the facing negative platelets repel each other, causing the montmorillonite to swell until, for all practical purposes, the individual platelets are dispersed. For this reason, fresh-water* damage is much more severe in sands containing montmorillonite than it is in sands containing other clays. Many investigators have shown that even trace amounts of montmorillonite can be responsible for marked reduction in the permeability of reservoir sands in the presence of fresh water." ." Monaghan and others have shown that fresh-water damage in montmorillonite-containing cores cannot be

Jan 1, 1965