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By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By J. E. Worthington, W. H. Spence, I. T. Kiff

Gold was discovered at the Haile mine in Lancaster County, South Carolina, in 1827 or 1828, and since that time the mine has been worked intermittently by both open-pit and underground methods until its forced closure in 1942 by World War II. Production figures are incomplete, especially for the early years, but the total gold produced is estimated to have been greater than 200,000 oz. Thus, the Haile mine has been the most productive gold mine in the eastern United States. The upper, residually enriched ores were relatively rich, but the bulk of the production has come from the mining of lower grade ores. General Geology The Haile mine is located in late Precambrian or early Paleozoic rocks of the Carolina slate belt at the edge of the Atlantic Coastal Plain [(Fig. 1)]. The metamorphic grade is lower greenschist facies and the rocks have been folded into a sequence of northeast-trending isoclinal folds. The gold is associated with siliceous, pyritic, and kaolinized felsic pyroclastic and tuffaceous rocks in an interbedded volcanic and volcanoclastic sequence of felsic to mafic tuffaceous rocks and argillaceous sediments [(Fig. 2)]. The ore bodies occur in two northeast trending zones approximately 500 m apart; each zone is 30-70 m wide and 600 m or more in length, with possible extensions to the east beneath the Coastal Plain sediments. Mineralogy. Gold in the Haile mine is always associated with siliceous and/or pyritic ores. The gold occurs in at least three states: As native gold as originally deposited; as residual gold derived from the breakdown of pyrite; and as gold included in pyrite. Major associated minerals in addition to quartz and pyrite are kaolinite, sericite, and iron oxides. Minor molybdenite, arsenopyrite, pyrrhotite, copper sulfides, sphalerite, rutile, and topaz are also present. Petrology. The gold-bearing ore zones vary from highly siliceous rocks to pyritic massive sulfide lenses. This variation is most easily seen today along strike from the Haile pit to the Red Hill pit. Ore grade material still exposed in the wall of the Haile pit consists of a highly siliceous and very thinly bedded rock containing minor pyrite. Along strike, the character of the mineralization changes to pyritic massive sulfide lenses occurring interbedded with siliceous horizons at the Red Hill pit. The siliceous rocks vary from the thinly-bedded material as just described from the Haile pit to silicified fragmental-appearing rocks to totally recrystallized cherty rocks lacking any recognizable primary features. Scattered, apparently at random, throughout the very thinly-bedded and very fine-grained ore face of the Haile pit are seemingly anomalous silica-rich clasts or concretions up to 5 cm in diameter which will be discussed later in this paper. Alteration. One of the most striking features of the Haile deposit is the alteration mineral assemblage which is intimately associated with the siliceous and pyritic ores. This altered material has been intersected in drill core at depths greatly exceeding the modern weathering profile and is, therefore, of hydrothermal origin rather than from supergene processes. This "sericite," actually a fine-grained mixture of sericite, kaolinite, and quartz, can be shown to stratigraphically underlie the gold- quartz-pyrite zone, and is well exposed in the open pit just southeast of the Haile and Bumalo pits. Relict textures indicate that this highly altered material was originally a felsic ash flow. Other similar alteration zones have been found in outcrop and drill core underlying the remaining ore bodies. Thus each of the mineralized zones consists of two parts: A siliceous and/or pyritic gold-bearing ore zone which is stratigraphically underlain by a zone of high alumina minerals, in this case sericite and kaolinite along with variable amounts of quartz. A green chrome mica, presumably fuchsite, is present in trace amounts in the high alumina zone. Genesis An adequate model to explain the origin and distribution of the gold deposits in the Carolina slate belt is presently lacking. Worthington and Kiff1 suggested a volcanogenic origin for certain gold deposits in the North Carolina slate belt from the waning exhalations of felsic volcanic piles. They also pointed out that such an origin has similarities to many epithermal precious metal deposits located in more recent volcanic piles in the western United States. A further key to the understanding of the genesis of the gold mineralization at the Haile mine is the close association of the mineralization in siliceous and sulfidic horizons to the genetically related and stratigraphically underlying high alumina alteration. Such high-alumina alteration is common around felsic volcanic centers in the Carolina slate belt and the mineralogy as seen today consists of some combination of kaolinite, sericite, pyrophyllite, kyanite, andalusite or sillimanite depending on the local prevailing grade of metamorphism. Accompanying the high-alumina alteration are large quantities of pyrite and iron-oxide minerals as well as characteristic minor accessory minerals often including base metal sulfides, fluorine-bearing minerals (topaz, fluorite, apatite), titanium-bearing minerals (ilmenite, rutile),

Jan 1, 1981

By Peter Stacey

This presentation provides comments on the increasing challenges associated with pit slope designs from the perspective of a design reviewer. Besides the technical issues related to the significant increase in current and proposed slope heights since the primary methodology in current use for pit slope designs was developed, other factors are coming into play. These include changes in mining equipment and associated operating practices, as well as a growing awareness on the part of mining executives and other stakeholders of the significance of stable, or at least well-managed, slopes. In the latter area, the associated clarification of responsibility has led to the increased use of either in-house or independent review consultants working on the behalf of management. From a technical perspective, since the mid-1970?s there have been significant improvements in the tools, particularly analytical methods, that are available to slope designers. There is also an increased understanding of the importance of a detailed geological model, with strong emphasis on alteration and/or structure to form the platform for the slope designs. However, the basic technology for determining the rock strength aspects has changed little, although an expanding body of experience is being accumulated in its use and there is a reasonable degree of comfort in its application for slope heights of up to at least 500 m. In addition, slope management is now viewed as a critical part of the implementation of slope designs and this has been supported by continuing improvements in slope monitoring systems. In recent years safety has become a primary concern, in part as a result of some major slope failures that have attracted the attention of regulators and the public, as well as mining executives, who are being held more responsible for unsafe conditions and associated events. There is therefore a growing demand for risk assessments to replace the deterministic design approaches upon which the current design technology is largely based. The focus of mine executives on safety has undoubtedly in part facilitated the recent long overdue revitalization of research into the design and stability of large pit slopes, the requirement for which has been recognized for many years by practitioners. This research, as well as the CSIRO Large Open Pit Study, will almost certainly provide advances beyond the empirical strength determination methods such as the Hoek-Brown failure criterion, which form the basis for current rockmass strength determination. At the same time, as mentioned above, there is a growing awareness of the requirement for a detailed structural model as a major component of every large slope design. In addition, other areas requiring further research include the impact of groundwater pressures on rock mass strength, particularly in rocks with low permeabilities, and the role of stress in high open pit slopes. From the perspective of design implementation, even with the recent significant advances in metal prices, mine operators remain under pressure to minimize mining costs. To address these constraints, mining equipment of ever increasing size is being introduced. There are, however, some disadvantages to this trend in the area of slope design. For example, the large electric shovels are not well designed for scaling bench faces, nor are they cost effective in this mode. As a result, specialized equipment may be needed in the mining cycle to perform the clean-up duties, which in turn increases operating costs. Further, where the large equipment is used in minimum width pushbacks to reduce the instantaneous stripping ratio, the advance rates can be high, but at the same time the associated changes in operating procedures are often not conducive to the concurrent use of such measures as controlled blasting, careful scaling and drain hole installation that generally improve stability. The resulting conflicts which may arise between the interests of production and those of slope stability are often exacerbated by the fact that these stabilization techniques actually increase the operating costs on which the operations manager is frequently judged, even though there is an overall increase in profit. Meeting the objective of developing slope designs which are practicable , i.e., achievable in terms of every aspect of the operating constraints in the specific pit, requires interaction and compromise between the geotechnical engineer, mine planners and operating staff during the formulation of the design criteria. In the current environment, it is often no longer sufficient to present slope designs in deterministic terms to a mine planner who accepts them almost without question. Increasingly, the requirement is that they be proposed within the framework of risk levels, related both to safety and to economic outcomes, to a decision maker who may not be a technical expert in the mining field. In this context, the mine executives must have sufficient information and understanding to be able to establish acceptable levels of risk for the company and other stakeholders; in this process the slope designers must play a major role. These changing requirements for presentation of slope designs necessitate clear communication of the basis for the design, which may be very complex, so that the implications of the designs may be thoroughly understood by all concerned. To ensure clarity at this stage, the slope designer must not only quantify the uncertainty in the input parameters, including the geological model, but must also be able to communicate and defend the resulting design recommendations. Where particular designs may have high associated risks, simply because of the degree of uncertainty in the data, this must also be recognized and proposed methods of reducing the uncertainty included in the presentation. In summary, from a reviewer?s perspective slope designs must not only be technically sound, but must also address the broader context of the mining operation as a whole, taking into account such factors as safety aspects, the available equipment to implement the designs, and the acceptable risk levels for the company. In addition, the designs must be presented in a way that will allow the mine executives, who are ultimately responsible, and the operators, who implement the designs, to fully understand the basis and short-comings of the designs and the risks associated with deviation from any constraints defined by the designer. It goes without saying that there must also be a well-defined monitoring system to confirm stability and detect and manage any variations in the design model or unexpected instability.

Jan 1, 2006

By P. N. Richards, M. K. Ormay

Commercially hot-rolled low-carbon steel strip may have one of two basic types of orientation texture, depending upon the amount of a iron which was present during the finishing passes. The changes in these textures with varying amounts of cold reduction up to 95 pct have been determined for the sheet surface plane and for parallel planes down to the mid-plane. The development of cold reduction textures has been reassessed on the basis of (200), (222). and (110) stereographic pole figures and pole density or inverse pole figure values. In agreement with the literature, it is shown that the textures can be described in terms of partial fiber textures but alternative descriptions are given for one of the fiber textures, in order to more closely correlate with experimental data. One partial fiber texture consists of orientations of the type (hkk)[011] extending from (100)[011] to {322}(011) in agreement with the literature. At moderate amounts of cold reduction, a second partial fiber texture forms with a <331> fiber axis inclined 20 deg to the sheet normal and a range of orientations centered on one close to (1 11)[112] and reaching to (232)[101] or (322)[011]. An alternative description involves a (111) fiber axis parallel to the sheet normal but capable of rotation about the rolling direction with rotation about the fiber axis. ORIENTATIONS developed in low-carbon steel strip after cold reduction are of commercial importance because they control, in part, the final preferred orientations after subsequent annealing. The method of control however is not understood completely. Some preliminary work indicated that the cold-reduced orientations and the subsequent annealing textures of commercial low-carbon steel were dependent on the orientations present in the material before cold reduction, that is, those present in the hot-rolled strip but, to date, the effects of initial orientations have not been extensively investigated. For this reason, much of the information given in the literature on development of preferred orientation is difficult to assess as details of initial texture and processing conditions are often inadequate or are altered by a subsequent heat treatment such as normalizing.&apos; It is known2 that anomalous results for near surface orientations may be obtained if lubrication during cold rolling is not adequate but whether lubricant was used during the experiments has not always been given, nor has the exact depth below the surface at which determinations have been made. A comprehensive review of cold rolling textures has been made recently by Dillamore and Roberts&apos; and more restricted recent reviews are due to stickels4 and Abe.5 Based largely on the experimental work of Bennewitz,1 reviewers have accepted that the preferred orientations produced on cold reducing low-carbon steel can be described in terms of two partial fiber textures as follows: Partial Fiber Texture A which has a (011) direction in the rolling direction and includes orientations within the spread from (211)[011] through (100)[Oll] to (211)[011.]; there is some controversy as to whether it extends as far as the orientation (111)[011]. As Dillamore6 has observed, the extent of this partial fiber texture depends on the intensity levels selected. Partial Fiber -texture B which has a (011) direction located 60 den from the rolling direction in the plane containing the rolling direction and the sheet normal. There are two directions which satisfy these conditions and orientations in this partial fiber texture extend from (21l)[0ll] through (554)[225] to (121)[101]. The orientations {211}(011) are members of both partial fiber textures A and B and it can be noted that a variant of {554)<225> is within 6 deg of a variant of {111}(112). Barrett7 had postulated earlier that, in addition to orientations which would fall into partial fiber texture A, a true fiber texture with a (111) direction in the sheet normal was present after heavy cold reduction. This fiber texture would include orientations such as {111}(011) and {111}(112). Later investigators, notably Bennewitz,&apos; have discounted this, mostly on the ground that the partial fiber textures A and B, as described above, contain all the strong orientations that have been observed. However in other work it has been reported2 that (222) pole density or inverse pole figure values show a continuing increase with increasing reduction by cold rolling and give values considerably greater than for any other low indices plane. Thus it could be inferred that a (111) fiber texture as described by Barrett would be one which becomes more dominant with increasing cold reduction, whereas Bennewitz&apos; concluded that components such as {554)(225) in partial fiber texture B began to decrease in intensity at high reductions. Following Bennewitz, one would expect a decreasing (222) pole density value (parallel to the sheet normal) with increasing cold reduction. Because fiber textures consist of grains with a range of orientations that have one axis in common, it has been inferred that during deformation the crystal orientations rotate about the fiber axis&apos;74 and that the orientations of crystals that at one stage belong to one fiber texture can rotate on further cold reduction into the other fiber texture through an orientation in which the two fiber textures intersect.&apos; For example,

Jan 1, 1970

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.&apos; reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,&apos; Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor&apos;s solution" within the restriction imposed by his assumptions. The essential features of Taylor&apos;s approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor&apos;s method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor&apos;s solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor&apos;s solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR&apos;S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

By G. R. Love, M. L. Picklesimer

Aboue 950°C the Nb-Zr system consists of a completely miscible bcc solid solution, commonly called the phase. Between 950 and 600°C, and between 20 and 85 pct Nb, the phase deconlposes, after sunciently long times, into two bcc solid solutions. The pct Zr alloys are conveniently descibecl with T-T-T (time-temperature-transformation) curves having a nose at about 2 hr at 700°C. The reaction rate varies only slowly with zirconium content and negligibly with oxygen contanzination; it is speeded up by a factor of 10 to 15 by 90 pct cold ulork and slowed dou by n factor oj 10 to 30 by a two-hundrecljold increase in grain size. Nb-r alloys with compositions between 40 and 85 pct Nb have been the basis for the majority of commercially important superconducting materials. In part because of their commercial promise, more is known about these alloys than about most other high-field superconducting materials. At the same time, there is considerable disputed or incomplete metallurgical information. For example, although Rogers and tkins&apos; indicate a monotectoid reaction at approximately 600°C and a two-phase 01 + 0, field extending between 20 and 85 pct Nb and to a maximum of 95OGC, erhout&apos; has reported that this entire region would be a single homogeneous B were it not for oxygen contamination. Again, although it has been shown that relatively short-time heat treatments in the vicinity of 700CZ significantly improve the ability of short wire samples to carry high currents in high magnetic fields at 4.2K, these observations have never been fully correlated with the structural change or changes occurring during the anneal. We intend to investigate in detail the effect of metallurgical variables, including heat treatment, on the superconducting properties of hard superconductors. To verify that our experimental techniques are valid and to establish a relative standard against which other materials may be measured, we feel it advisable to know the behavior of the Nb-Zr alloys under a variety of processing conditions. As an initial step toward this goal, we have determined in detail the kinetics of the transformations in Nb-Zr alloys. EXPERIMENT A number of problems had to be solved before beginning any fruitful work on the reaction kinetics in this system. While solving some of these problems, either by chance or by design, small amounts of information were obtained about alloys containing 40, 50, 60, 65, 67, 70, and 75 pct Nb, bal. Zr. In addition, a large range of grain sizes and a range of temperatures considerably greater than the range indicated by Rogers and Atkins phase diagram were examined. We will, however, report in detail only the results obtained for the Nb + 33 pct Zr and Nb + 25 pct Zr alloys at three grain sizes, two levels of oxygen contamination, and the temperature range 550 to 950°C. These data are most complete, but the other data are sufficiently complete to indicate the kind and magnitude of the variation of the transformation kinetics outside this range. The first and most difficult problem encountered in this inquiry was one of sample homogeneity. When Nb-Zr alloys are arc- or electron-beam-melted on a cooled copper hearth, solidification is sufficiently slow that there is appreciable coring in the cast structure and a large variation of grain size across the button thickness. Both these factors significantly affect the apparent reaction rate in the system. A two-step solution to the problem was attempted; an arc-melting and drop-casting technique has been developed by conald that greatly reduces the as-cast grain size and virtually eliminates coring segregation. Ingots made in this way exhibited no detectable (3 pct maximum) zirconium segregation. Before it was evident just how good this technique was, we attempted to supplement it with rather long-time, high-temperature annealing of the cast ingots. This annealing was carried out in evacuated and sealed (seal-off pressures < 1.0 x 106 torr) quartz capsules lined with tantalum foil at 1400 to 1450 C for 8 to 72 hr. There were two principal effects of this treatment: the grain size increased to a fairly uniform 150 p, and the surface and all grain boundaries near the surface acquired a film of a second phase, tentatively identified as an oxide (possibly additionally contaminated with silicon). There was no evidence that this 1400 C treatment had affected the zirconium segregation. High-temperature annealing was subsequently used only for grain-size control, but anneals of longer than 4 hr at temperatures greater than 1000°C were performed in dynamic vacuums (pressure no greater than 1.0 x lo torr). Any contamination resulting from these treatments was well below the limits of detection of our techniques. All samples, as cast, were cold-swaged to at least 85 pct reduction in area. The samples called cold-worked were tested as swaged. The minimum re-crystallization anneal for these alloys was about 12 hr at 1050 C; this produced an equiaxed grain diameter of about 4 to 8 P. Annealing for 4 hr at 1450°C produced a grain size of about 80 to 150 p; and annealing for 4 hr at 1650aC, close to the melting point of many of these alloys, produced a grain size of 0.5 to 1.0 mm. At all temperatures, the larger grain size was

Jan 1, 1967

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith&apos; while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith&apos;s experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours&apos; exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By Joyce A. Ober

Minerals for electronic and optical uses divide easily into two sections: 1) quartz and 2) minerals other than quartz. QUARTZ The properties of quartz crystal that make it useful for radio communications were discovered in 1918. Since that time, an in¬dustry for the mining and processing of natural quartz crystal has grown, matured, and been almost entirely replaced by new tech¬nology. The new technology still involves quartz crystal, but ma¬terial that is grown rather than mined. An economic summary of the commercial growing of quartz crystals has a place in a handbook directed to the mineral engi¬neering industry because quartz crystals have long been an impor¬tant commercial mineral, and the raw material for cultured quartz - ¬that is to say, quartz crystals grown through the ingenuity of man - is still natural quartz. Nearly all the natural crystals that have been used for elec¬tronics and optics came from Brazil. The larger pieces which met rigorous standards of quality were used for electronic and, to a lesser extent, optical components. Smaller pieces and fragments were used for vitreous silica. The need for high quality material in quantity led to US government sponsored research and exploration programs in the 1940s. No deposits meeting the very rigid requirements for electronic-grade quartz were found, but other projects resulted in the development of a process for the factory growth of beautiful crystals of prescribed shape, size, and quality. Domestic deposits of appropriate quality were identified to use as raw materials for the quartz culturing process. The development of the cultured quartz crystal illustrates the success that technology can have in adapting a product of the mine to increasingly sophisticated uses. A remarkable achievement per¬haps, but foreshadowed by experiments by Giorgio Spezia (1908), an Italian geologist studying the relative effects of temperature and alkaline environment on the solubility of quartz. Modem radio equipment is most often controlled as to fre¬quency by the presence in the circuit of a separately added crystal¬ - the 1918 discovery responsible for the existence and growth of the quartz industry. The crystal is quartz, but this component is a carefully oriented and prepared slice from a crystal, but not a crystal as recognized by a rock hound or seen in a museum. How quartz operates to control frequencies is not a proper subject for a handbook on industrial minerals, and references should be consulted (Cady, 1964, Mason, 1964). Quartz belongs to a class of materials called dielectrics: those that do not conduct an electric current but permit electric fields to exist and act across them. Quartz shows the piezoelectric effect, which means that when a quartz plate is mechanically deformed against its natural stiffness, one of its surfaces becomes negatively charged, the other positively charged. When the plate is released quickly from the stress, the charges disappear as the plate regains its original shape, but because of mechanical momentum the plate deforms in the opposite direction (to a lesser amount) and the surfaces correspondingly become charged in the opposite direction. By thinly coating the two surfaces with metal and attaching flexible wires, these charges can be brought into an electronic circuit. If the surfaces are suddenly electrically charged by movement of current through the wires, the converse piezoelectric effect occurs and the plate deforms. Carry the thought further and it is realized that an alternating current flowing through the wires responds to the mechanical oscillation. By controlling the thickness of the plate, its mechanical vibration frequency can be varied through a wide range. One type of quartz plate, the AT-cut, has a precisely defined orientation with respect to the crystallographic axes of the crystal and vibrates on a microscopic scale much as a book would deform when placed flat on a table and the top cover moved parallel back and forth with the hand. At least 17 other orientations have been studied, some of which have preferred uses in various applications (Cady, 1964). The quartz crystal industry is composed of three main segments (excluding fused quartz and quartz used for optical purposes): 1. Natural electronic-grade quartz crystals. Mined quartz suitable for fabrication into piezoelectric units. Zlobik (1981a) esti¬mated the waste to ore ratio at 1:1000 to 1000 000, depending upon the deposit. 2. Lasca. Mined quartz usable as feedstock in the production of cultured quartz. Approximately 0.63 kg of lasca are required to produce 0.45 kg of cultured quartz. 3. Cultured quartz. Cultured quartz is produced from lasca feed¬stock in a process of crystal growth in an autoclave under conditions of heat, pressure, and time. It is estimated that 0.45 kg of cultured quartz is equivalent to 1.4 to 4.5 kg of natural quartz crystal in yield of commercial quartz suitable for slicing into piezoelectric units. The chronology of the development of the quartz crystal industry both natural and cultured follows: Date Comment 1918 Discovery of the piezoelectric effects of quartz crystal 1921 Application of the piezoelectric effects of quartz crystal in the circuitry of radios 1948 Establishment of a quartz crystal commodity stockpile by the US Government 1952 US consumption of natural quartz crystal at an all time high of 228 t 1958 First commercial production of cultured quartz crystal 1970 Cultured quartz crystal production exceeds imports of nat¬ural quartz crystal 1971 Cultured quartz crystal consumption surpasses natural quartz crystal consumption

Jan 1, 1994

By E. A. Martell, K. S. Sweder

INTRODUCTION Lung cancer in uranium miners has been attributed to alpha irradiation of basal cells of the bronchial epithelium by radon daughters, primarily by 7.7 MeV alphas from polonium-214 (Altshuler et al., 1964). It also has been was observed that for a given cumulative radon progeny exposure, uranium miners who smoke cigarettes have an incidence of lung cancer about 10 times higher than nonsmoking miners (Lundin et al., 1969). It has been pointed out that the large excess of lung cancer deaths among smoking uranium miners is a multiplicative effect (Doll, 1971), which suggested possible synergistic interactions between airborne radon progeny and cigarette smoking. Experimental studies of the complex pattern of interactions between radon progeny, cigarette smoke particles, and the cigarette smoking process are in progress in our laboratory. Preliminary results, reported elsewhere (Martell, 1981), implicate alpha radiation from indoor radon progeny in the etiology of lung cancer in all cigarette smokers. Cigarette smoking produces high concentrations of smoke particles of low mobility and respirable size--particles between 0.5 and 4.0 µm in aerodynamic diameter (see below). The attached fraction of indoor radon progeny is highly dependent on the air concentration of small particles from cigarette smoking and from other combustion sources (Martell, 1981). The size distribution and other properties of radon progeny associated with cigarette smoke particles enhances their effectiveness in the induction of bronchial cancer in man. In this paper we discuss the properties of radon progeny associated with cigarette smoke, the fractionation of radon progeny and modification of their aerosol properties in burning cigarettes, the role of 218Po in these processes, the production of insoluble 214Pb and 212 Pb enriched particles in burning cigarettes, and the consequent differences in the patterns of polonium isotope alpha irradiation in the bronchial epithelium of smokers. EXPERIMENTAL PROCEDURES Experimental methods used in these studies involve the use of small experimental chambers of known radon and radon progeny concentrations in combination with aerosol collection and sizing techniques and sensitive radioactivity detection methods. The use of low-level [ß-] counting for radon progeny determination, providing a measure of 214 Pb plus 214Bi activity, makes it possible to carry out chamber experiments with small radon emanation sources and relatively low air concentrations of radon and radon progeny concentrations in the range from 100 to 1,000 pCi per liter. Thus, for example, in a typical experiment we use a 10 nanocurie 226Ra solution standard in a 10 liter chamber, providing an equilibrium concentration of 1,000 pCi of radon per liter. In small sealed chambers, radon progeny plate out rapidly on the chamber walls, with steady-state concentrations of airborne progeny less than 2 percent of equilibrium levels. This is experimentally convenient because, upon introduction of high concentrations of cigarette smoke particles or small particles from other sources, there is a systematic ingrowth of attached radon progeny, providing a tagged aerosol source of known age and radon progeny composition. In some chamber experiments a 226Ra solution standard of small volume, acidified to O.1N HNO3, was used as the radon emanation source. When used with a bubbler the holdup of radon in an 8 ml volume of 226Ra solution standard at 0.1N HN03 was only 2% of the total radon in the chamber at equilibrium. For experiments with 212Pb-tagged aerosols, we used a dry Ba(228Th) stearate emanation source prepared by the method of Hursh and Lovaas (1967). 226Ra and 222Rn determinations were made by radon gas counting. The 222Rn in a sealed air or water sample is transferred, using helium gas as a carrier, successively through a dry ice cooled trap at -80°C to remove water, through ascarite to remove C02, and through a small activated charcoal trap at -80°C to collect the 222Rn. Subsequently, by heating the charcoal to 400°C, the 222Rn is transferred next to an LN2-cooled capillary trap, and finally into an alphascintillation counting cell of the type described by Lucas (1957). As already stated, radon progeny activities were determined by low-level [ß-] counting, which provides a measure of 214Pb plus 214Bi. The radon progeny samples, collected on efficient Delbag polystyrene micro-fiber filters or on impactor foils, are placed in close, sandwich geometry between two thin-walled flow counters inside shielding anticoincidence counters and a 15 cm thickness of steel shielding. This configuration provides nearly 4II geometry and a low background of only 0.25 to 0.30 cpm. Aluminum absorber was added to provide a combined thickness of absorber and counter wall exceeding 7.0 mg/cm2 to eliminate the variable contribution of 7.7 MeV alphas from 214Po. 212 Pb determinations also were carried out by low-level [ß-] counting, in this case using a combined absorber and counter wall thickness of 9.0 mg/cm2 to eliminate contribution of 8.8 MeV alphas of 21 Po. In each experiment the [ß- ]activity data were corrected for decay to an appropriate common reference time for assessment of activity distributions.

Jan 1, 1981

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the &apos;a; and &apos;c,,&apos; edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.&apos; LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By T. R. A. Davey

IN 1947 the author became interested in the fundamental aspects of the desilverizing of lead by zinc, conducted some experimental work, and searched the technical literature for all available fundamental data. Since then a revival of interest in the subject in Europe resulted in the appearance of quite a number of papers. It became evident that it would be more profitable to collect together and examine thoroughly the results of various workers, than to attempt to duplicate the experimental determinations. There are many inconsistencies in the various publications, and it is opportune to review at this time the present status of knowledge on the Ag-Pb-Zn system. There is also a need for a clear description, in fundamental terms, of the various desilverizing procedures. This paper is presented in four sections: 1—There is an historical review of the origins of the Parkes process, of the results of many attempts to find a satisfactory fundamental explanation for the phenomena, and of the modifications proposed to date. 2—A diagram of the Ag-Pb-Zn system is presented. This is believed to be free of obvious inconsistencies or theoretical impossibilities, although thermodynamic analysis subsequently may reveal errors. 3—The fundamental bases of the various desilverizing procedures, which have been used up to the present day, are described; and a new method is suggested for desilverizing a continuous flow of softened bullion in which the bullion is stirred at a low temperature in two stages producing desilverized lead at least as low in silver as that from the Williams continuous process and a crust which, on liquation, yields a very high-silver Ag-Zn alloy. 4—A suggestion is made for the revival of de-golding practice, following a recently published account which does not seem to have attracted the attention it deserves. The terms "eutectic trough" and "peritectic fold" as used in this paper are synonymous with "line of binary eutectic crystallization" and "line of binary peritectic crystallization" as used by Masing.&apos; The German literature on ternary and higher systems is rather extensive and a fairly general system of nomenclature has arisen, whereas in English usage the corresponding terms are not as well established. For this reason the meanings of terms used in this paper, together with the equivalent German terms, are given as follows: 1—Eutectic trough—eutektische rinne: line at which a liquid precipitates two solids S1 and S2 simultaneously. If the composition of a liquid which is cooling reaches this line, it then follows the course of this line until a eutectic point is reached, or until all the liquid is exhausted. The tangent to the eutec-tic trough cuts the line joining S1S2. 2—Peritectic fold—peritektische rinne: line at which a solid S1 and a liquid L transform into another solid S2. If the composition of a liquid which is precipitating S1 reaches the line, on further cooling only S2 is precipitated. The liquid composition moves from one phase region (L + S1) into the other (L + S2), and does not follow the course of the boundary. The tangent to the peritectic fold cuts the line S1S2 produced nearer S,. 3—Liquid miscibility gap, or conjugate solution region—mischungslucke: the region within which two liquid phases coexist in equilibrium over a certain range of temperature. A system whose composition is represented by a point in this region comprises one liquid at high temperature; then as the temperature is progressively reduced, two liquids, one liquid and one solid, one liquid and two solids, and finally three solids. 4—Liquid miscibility gap boundary—begrenzung der flussigen mischungsliicke: the line along which the surface of the miscibility gap dome, considered as a solid model, intersects the surrounding liquidus surfaces. 5—Tie lines—konoden: lines joining points representing the compositions of two liquids, a liquid and a solid, or two solids, in equilibrium. In binary systems the only tie lines customarily drawn are those through invariant points, e.g., through the eutectics of the Pb-Zn and Ag-Pb systems, or the various peritectics of the Ag-Zn system, as in Figs. 1 to 3. In ternary systems it is desirable to draw sufficient tie lines to indicate the slopes of all possible tie lines. 6—Ternary eutectic point—ternares eutektikum: point at which liquid transforms isothermally to three solids, S1, S2, and S Such a point can lie only within the triangle 7—Invariant peritectic (transformation) point— nonvariante peritektische umsetzungspunkt: (a) — On the miscibility gap boundary, the point at which two liquids and two solids react isothermally so that L, + S, + L, + S2. (b)—On the eutectic trough, the point at which a liquid and three solids react iso-thermally so that L + S, + S2 + S3. Such a point must lie on that side of the line joining S,S which is further from S,. (c)—A further possibility, not found in this ternary system, is that the point is at the intersection of two peritectic folds when the reaction concerned is L + S, + S, + S Historical Introduction Karsten discovered in 1842 that silver and gold may be separated from lead by the addition of zinc.2 Ten years later Parkes used this fact to develop the well known desilverizing process which bears his

Jan 1, 1955

By James W. Dally, William L. Fourney, Anders Ladegaard Peterson

For the past 3 years, the authors have been conducting research sponsored by the National Science Foundation (RANN) to improve the process of excavation by drilling and blasting. The approach followed has been experimental where the development of stress waves and fractures initiated at the bore hole have been investigated in order to obtain a complete understanding of the dynamic fracture process. The second step in the approach has been to introduce modifications in the drill and blast procedure which will permit closer control of the fracture process. The laboratory investigations involve high speed photography where the dynamic fracture process is recorded with a Cranz-Schardin 1, 2 multiple-spark camera. The camera is equipped with 16 spark gaps which are pulsed at 25 K volts to produce an intense but very short (0.5 sec) flash of light. The camera is capable of recording 16 photographs of a dynamic event at framing rates which can be varied from 30,000 to 1,500,000 frames per second. The exposure time is sufficiently short to stop motion associated with detonating explosive charges and to make visible the details of the fracture process at a bore hose. The bore hole in a massive intact rock formation is modelled with a two dimensional plate containing a circular hole to represent the bore hole. The model material employed is a transparent polyester known commercially as Homalite 100.* This polymeric material is extremely brittle as evidenced by its extremely low fracture toughness of [ ]. The fracture toughness is a measure of the ability of a material to resist the propagation of flaws or small cracks. In comparison, Schmidt3 has recently measured the fracture toughness of Salem limestone and determined [ ]. Thus, the Homalite 100 should closely model the brittle nature of rock where fractures occur at small flaws and propagate without any apparent plastic deformation. Homalite 100 is also birefringent, which indicates that it becomes optically anisotropic when subjected to either static or dynamic loads. Circularly polarized light is transmitted through the loaded Homalite 100 model in a polariscope4 and the birefringence produces an optical interference pattern which is called a fringe pattern. For dynamic photoelasticity, the multiple-spark camera is equipped with polaroid filters to produce the circularly polarized light required to generate the photoelastic fringe patterns. An example of a singlespark frame showing a fringe pattern from a typical experiment is presented in [Fig. 1]. The photograph was taken 0.000072 sec (72 sec) after the detonation of the explosive charge. The circular fringes are due to the outgoing dilatational or P type stress wave and travel with a velocity of 85,000 in. per sec (2260 m/sec) in the Homalite 100. The P wave is followed by a second lower velocity stress wave known as the shear or S type wave which propagates at a velocity of 49,000 in. per sec (1245 m/sec). In the local neighborhood of the bore hole, several radial cracks are visible. These cracks propagate at essentially a constant velocity of 15,000 in. per sec (380 m/sec) prior to arrest. The fringes about the crack tips and in the local region of the bore hole are primarily due to the residual gases contained in the bore hole after the explosive charge was detonated. Sixteen frames similar to this one are recorded during the experiment to give full field visualization of the dynamic event at 16 discrete times over its duration. The fringe order number N is related to the difference in the principal stresses of and 02 according to a stress optic law4: [ ] where f0 = material fringe value, and h = model thickness. The wholefield dynamic-fringe patterns provide a basis for simultaneously observing the interaction between propagating cracks and the stresses which drive these cracks. Fracture Control Experiments Improvements in the efficiency of the drill and blast procedures must involve close control of the fracture process following the detonation of an explosive charge in a bore hole. By control it is implied that the number of cracks initiated and the location of each crack on the wall of the bore hole can be specified. Control also, involves orienting each crack and maintaining the crack path and velocity until the specified crack length is achieved. If the entire fracture process can be controlled, then rounds can be designed to optimize volume removed. fragment size and minimize costs. One area of blasting where fracture control is vitally important is in underground excavation where the strength and stability of the rock walls must be maintained and smoothness and precision of the walls must be achieved. The smooth blasting method is one of the most commonly employed procedures for achieving some degree of fracture control. In smooth blasting, the central region of material is first removed, and then the final row of closely spaced undercharged or cushioned holes are fired to remove the final volume and produce a smooth wall. In some instances, unloaded or dummy holes between the loaded holes are recommended to guide the fracture plane. This investigation pertained to an evaluation of 3 features of the smooth blasting process. These included (a) the effect of stress reinforcement on fracture by simultaneously firing 2 charges; (b) the influence of a dummy hole on control of the fracture planes between 2 simultaneously fired charge holes; and (c) the influence of dummy hole spacing on fracture plane control.

Jan 1, 1979

By A. Y. Bethune, W. G. Woolf

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By F. W. Schremp, V. L. Johnson

This paper discusses the results obtained from high temperature, high pressure filter loss studies in which field samples of clay-water, emulsion, and oil base fluids were used. High temperature, high pressure tests of some premium priced emrilsion and oil base drilling fluids show filter loss peculiarities that are not predicted by standard API tests. It is recommended that high temperature, high pressure filter loss tests be used to evaluate the performance of such fluids. Apparatus is described which proved to be satisfactory for evaluating filter loss behavior over a wide range of temperatures and pressures. INTRODUCTION The petroleum industry spends large sums of money each year on chemical treating agents for lowering filter loss and on premium-priced low filter loss drilling fluids. While it is an accepted fact that low filter loss is advantageous during drilling operations, it is questionable whether the present standard method of determining filter loss gives a reliable indication of the loss to he expected under bottom hole conditions. The purpose of this paper is to show that high temperature. high pressure filter loss tests Should be used to evaluate filter loss behavior of fluids for deep drilling. Concern over possible effects of filter loss on oil well drilling and well productivity dates back to the early 1920&apos;s. During the years 1922 to 1924, filtration studies were reported by Knapp,&apos; Anderson2 and Kirwan." These studies were the first to be reported in the literature on this subject. No further information was published on the subject until 1932 when Rubel&apos; presented a paper in which he discussed the effect of drilling fluids on oil well productivity. In 1935. .Jones and Babson constructed the first laboratory tester designed to study the effects of temperature and pressure on the filter loss behavior of clay-water drilling fluids. In a discussion of their investigations, Jones and Babsons stated, "Performance characteristics of a mud can he evaluated with considerable reliability by a single test at 2,000 psi and 200°F. Exact correlation between the results of performance test5 made under these conditions and the behavior of muds in actual drilling operations is of course impossible." Jones arid Babson apparently were well aware that at best laboratory tests can give only qualitative answers to the question of what is the actual behavior of a drilling fluid when subjected to deep drilling conditions. Jones&apos; presented a paper in 1937 in which he described a static filter loss tester to be used for routine filter loss tests. This instrument subsequently was adopted as the standard APl filter loss tester. In 1938, Larsen7 developed a relationship between filtrate volume and filtrate time that is in general acceptance today. Larsen was cognizant of the danger of estimating bottom hole behavior from filter loss measurements at room temperature. He tried to predict the effect of temperature on filter loss by relating temperature effects through the temperature dependence of filtrate viscosity. This was undoubtedly an over-sirriplification of the temperature dependence of drilling fluid filter loss. In 1940, Byck" published a summary of experimental results of filter loss tests made on six representative California clsy-water drilling fluids. He concluded that "no existing method will permit even an approximate determination of the filtration rate at high temperature from data at room temperature. It is necessary to measure filtration at the temperature actually anticipated in the well, or to make a sufficient number of tests at various lower temperatures so that a small extrapolation of these data to the anticipated well temperature may be applied." Byck&apos;s findings were presuma1)ly well accepted and recognized by drilling Fluid technologists, and yet, they did not lead to wide adoption of high temperature drilling fluid filtration equipment. This is evidenced by the fact that no addition information has appeared in print on the subject since 194). Study of Byck&apos;s data shows that there was a useful consistency in them. The fluids did not show predictable losses at high temperatures, but they did line up at high temperatures in approximately the same order that they lined up at low temperatures. That is, if a fluid appeared to be a good fluid with relatively low loss at low temperatures, it would also be a good fluid with relatively low loss at high temperatures. In the last decade. the above situation has changed. The drilling fluid art is markedly different from what it was. The outstanding change, as far as the present discussion is concerned, has been the adoption of wholly new types of drilling fluids. Oil base and emulsion drilling fluids have come in to wide use. It is, therefore, necessary- to re-examine previously satisfactory generalizations to see if they are still valid. It turns out. as might have been expected. that Byck&apos;s explicit generalization. already quoted, is still true. Filter losses at high temperatures cannot be predicted from filter losses at low temperatures. However, no further generalizations are valid now. Fluids of different chemical types show different general behaviors. No longer do the fluids line up approximately the same at high temperatures as they do at low temperatures. They may line up entirely differently. Special fluids exhibiting very low loss at low temperatures may have losses as high as those of ordinary clay-water fluids at high temperatures. This fact is highly significant, because premium prices are being paid for the special fluids.

Jan 1, 1952

By Robert H. Merrill

INTRODUCTION In most cases, the design of an underground mine is based upon the premise that the ground either will cave or will be stable. This chapter concerns the design of a mine in ground that will cave readily or with some as¬sistance, such as by long-hole drilling and blasting. Some of the more widely used caving systems of mining are panel caving, block caving, sublevel caving, and large pillar recovery. Some of the less widely used systems are glory-hole, top slicing, and induction caving. Al¬though the common practice of pillar robbing is not usually considered to be a caving system, this subject will be treated as a part of this chapter. BASICS OF CAVING Caving systems are most successful in ground that will cave in sizes that will flow through openings and grizzlies, and will easily load in cars or on belts for haul¬age. The ground most likely to cave well is highly frac¬tured and contains breaks, flaws, or other discontinui¬ties that form planes of weakness. Also, caving action can be greatly enhanced if the host rock itself is low in compressive, shear, and tensile strength. Ideally, a cav¬ing system of mining is best employed when the criteria for caving is a feature of the ore body and the develop¬ment drifts, haulageways, and drawpoints can be mined in a highly competent rock beneath the mineralized zone. However, the development is often in the same, or similar, fractured rock and the openings require sub¬stantial artificial support to assure stability. Several clues can be assembled to identify potential caving ground; however, for borderline cases, no sure method has been devised to date. The diamond-drill cores taken for exploration can provide an excellent clue provided drilling is performed carefully by experienced drillers. For example, if the ground is cored in such a manner that the breaks in the core are caused more by failure of the rock than by whipping core barrels, plugged drill bits, or other drilling causes, and the intact core lengths are consistently long [say, 0.6 to 3 m (2 to 10 ft) of unbroken core], there is little reason to believe the ground will cave without considerable as¬sistance. This is especially true for rocks with compres¬sive strengths above 34.5 MPa (5000 psi) and tensile strengths above 2.1 MPa (300 psi). On the other hand, if core recovery is low (below 80%) and the recovered ore is broken in small pieces and the breaks are along obvious weaknesses in the rock, the chances are excel¬lent that the ground will cave. This is true even when the rock between the defects has high compressive and tensile strength. Another clue has already been mentioned, that is, the measurement of the physical properties of the rock and the natural planes of weakness or defects in the rock. The planes of weakness in the rock can often be detected from outcrops, cores, or other exposures of the rock under consideration. Some rock types are known to be strong and will sustain large, unsupported open¬ings and would be difficult to cave intentionally. Yet the same rock type can also contain unbonded or weak planes of weakness or fractures, and in these locations the rock would undoubtedly cave with little assistance. Therefore, although the inherent strength of the rock is a factor in caving, the natural defects in the rock are more often the deciding factor. DESIGN CONCEPTS For the most part, the design of openings for caving ground is a problem of the interaction of openings over a relatively large area of the mine. To illustrate, Fig. 1 is a simplified section of a series of openings along the grizzly level or draw level of a block caving or panel caving development, and above this opening is a simpli¬fied section of a room-and-pillar arrangement on the undercut level. At this stage of the development, the stresses around the openings on the grizzly level are only moderately influenced by the openings on the undercut level and vice versa. Therefore, the stresses around the openings are approximated by the stresses around single or multiple openings in rock, the values of which are de¬scribed in the literature (Obert, Duvall, and Merrill, 1960; Obert and Duvall, 1967). Once the pillars on the undercut level are blasted (Fig. 2), the situation changes abruptly. The undercut opening (prior to caving) now can be approximated as an ovaloidal opening above the grizzly drifts and this opening tends to shield the vertical stress field. As the caved stage is drawn the stope approximates a much larger rectangular or square opening filled with rock, and if the rock is not sustaining a major portion of the stress field, this opening can be considered (for en¬gineering purposes) to be empty and the stresses that interact between the larger and the smaller openings take on a totally new perspective (see Fig. 3). Next, let the material cave to the surface, and let the caving ma¬terial sustain some stress, but much less than if the ma¬terial were intact. This condition is similar to a soft inclusion in a rigid body and has been treated in the literature (for example, Donnell, 1941). At this point in time, the grizzly drifts are subjected to the stress con-

Jan 1, 1982

By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.&apos;-&apos; It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer&apos; has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953

By C. R. Barker, D. A. Summers, H. D. Keith

Introduction Historically, the presence of methane has been a problem, mainly in and around the working areas of active coal mines, and only in these areas has drainage been considered. Drainage, where practical, has been achieved through the drilling of holes forward into the coal and the surrounding strata from the working area. These holes generaly have been short in length, although where methane drainage operations around a longwall face have been undertaken, the holes have had to be longer in order to adequately drain from the center of the face into the access gate roads. In recent years, attempts have been made to degasify the coal seams in advance of mining, without disruption of the mining cycle. This is done by drilling much longer horizontal holes through the coal in advance of the working area. Under the aegis of the federal government, methods have also been developed for draining coal seams of their methane content in advance of mining, but from shafts sunk from the surface, without using the active area of the mine as the location for the drill holes. Development of methane drainage has recently been encouraged by the potential use of the drained methane as a commercial energy source, with a need, therefore, to adequately organize a collection system, separate from mining the seam for coal. This has already been successfully accomplished, for example, in the Federal No. 2 mine of Eastern Associated Coal Corp. starting in 1975 (Johns). However, whether the system gains access to the coal through horizontal drilling from a pre- existing mine or via access through a separate shaft from the surface, long horizontal holes are required to adequately tap the methane reserve. It is to this regard-the actual drilling of the horizontal holes-that this paper is directed. It will examine potential benefits that may accrue, both in conventional horizontal hole drilling from a mine site underground, and also in drilling from the surface if a high pressure water jet drill is used to drill the degasification holes. Long Hole Drilling from an Underground Site Personnel from the Bureau of Mines have recently examined methods for conventional drilling of long horizontal holes to gain access for methane drainage. They have shown that it is possible (Cervik, Fields, and Aul) to drill out some 610 m using a conventional drilling system. Three types of bit were used in the program and by alternating between a drag bit, tricone bit, and plug bit, advance rates of between 0.6-3.6 m/min were achieved. Hole diameters varied from 7.6-9.2 cm in surface tests at bit thrusts of 1360 kg. A hole was then drilled and maintained in relative alignment within the coal seam for a distance of 640 m. Thrust levels had to be lowered to between 363-680 kg across the bit. Because the loads were smaller than those used in the surface trial, advance rates in the hole were of the order of 10-38 cm/min. The thrust level was lowered since it was found that the level of the thrust controlled the inclination of the drill so that, for example, a thrust of 363 kg caused the hole to incline downward, while at greater than 544 kg the hole inclined upward with the 9-cm-diam bit. Thrust levels increased 227 kg when the hole diameter was raised to 9.2 cm, although in such a case penetration rates in excess of 56 cm/min could be achieved. Horizontal Water Jet Drilling of Coal The University of Missouri-Rolla has recently undertaken research for Sandia Laboratories on the use of high pressure water jets as a means of drilling through coal. The initial experiment in this program called for drilling a hole horizontally into a coal seam from the side of a strip pit using water jets as the cutting mechanism. A very simple setup [(Fig. 1)] was used in this program and a 15-m hole was drilled at an approximate drilling speed of 1.2 m/min. The nozzle was designed so that the hole dimension was approximately 15 cm across [(Fig 2)] and the thrust was maintained at levels below 91 kg in moving the drill into the coal face. The system used was very crude and comprised a high pressure water jet drill enclosed within a 5.7-cm outer diameter galvanized water pipe to provide rigidity to the drilling system. This pipe sufficed to maintain hole alignment over the 15-m increment. While it is premature to make long-term predictions on ultimate applicability of this sytem to long hole drilling, certain inherent advantages of water jets can be delineated from research results and suggest considerable advantage to further research in development of this application. High pressure water was supplied at approximately 62 046 kPa from a 112-kW high pressure pump, with a 83 L/m flow through the supply line to the nozzle. The drilling system consisted of a nozzle rigidly attached to the front end of the galvanized piping. High pressure fluid was supplied to this nozzle through a flexible high pressure hose that fed from the nozzle back through the galvanized pipe to a rotary coupling attached

Jan 1, 1981