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By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By James H. Courtright, Kenyon Richard

SILVER Bell is situated 35 airline miles northwest of Tucson, Ariz., in a small, rugged range rising above the extensive alluvial plains of this desert region. Its geographical relation to other porphyry copper deposits of the Southwest is shown on the inset map in the lower left corner of Fig. 1. The climate is semi-arid. Altitudes range within 2000 and 4000 ft. Opening of the Boot mine, later known as the Mammoth, in 1865 was the first event of note in the district's history. Oxidized copper ores containing minor silver-lead values were mined from replacement deposits in garnetized limestone and treated in local smelters. Copper production had approached 45 million pounds by 1909 when the disseminated copper possibilities in igneous rocks were recognized. Extensive churn drill exploration carried out during the next three years resulted in partial delineation of two copper sulphide deposits, the Oxide and El Tiro. Although the then submarginal tenor discouraged exploitation of these disseminated deposits, selective mining of orebodies in the sedimentary rocks continued intermittently until 1930, providing a production total of about 100 million pounds of copper. The American Smelting & Refining Co. began exploratory and check drilling in 1948 and subsequently made plans for mining and milling the Oxide and El Tiro orebodies at the rate of 7500 tons per day. Production began in 1954 at a rate of about 18,000 tons of copper annually. Formations ranging in age from Pre-Cambrian to Recent are exposed in the Silver Bell vicinity. The more erosion-resistant of these, Paleozoic limestone and Tertiary volcanics, predominate in the scattered peaks and ridges comprising the Silver Bell mountains. The porphyry copper deposits are located along the southwest flank of these mountains in hydrothermally altered igneous rocks. These are principally intrusives which cut Cretaceous and older sediments and are considered to be components of the Laramide Revolution. For three-fourths of its length the zone of alteration strikes west-northwest, Fig. 1. There now is no single structure that accounts for this alignment. However, indirect evidence suggests that a fault representing a line of profound structural weakness existed in this position prior to the advent of Laramide intrusive activity. This line will be referred to as the major structure. It was obliterated by the Laramide intrusive bodies but exerted a degree of control on their emplacement, as evidenced by their shapes and positions. The influence of fault structures on the shapes of intrusives in other porphyry copper districts has been noted by Butler and Wilson' and by others. As shown on the inset map on Fig. 2, a fault of parallel trend and considerable displacement lies to the north. This fault is now marked by a line of small Laramide intrusive bodies. To the south is a third fault of large displacement. Evidence of its age in relation to the Laramide intrusions and mineralization is not recognized, but its conformance in strike with the other two major faults is significant. These three breaks establish a pronounced trend of regional faulting. They are high-angle, and the southerly one may be reverse, Stratigraphic separations on these faults are of the order of several thousand feet. The local Paleozoic section is about 4000 ft thick. It is composed predominantly of limestone with a basal quartzite member. The Cretaceous section appears to exceed 5000 ft. Conglomerates, red shales, and arkosic sandstones (the youngest) characterize the three principal members. Intrusion of alaskite marked the beginning of Laramide igneous activity. It was emplaced as an elongate stock with one side closely conforming to the major structure line throughout a distance of nearly 4 miles. The alaskite was at one time regarded as a thrust block of pre-Cambrian rock'; however, its intrusive relationship and consequent post-Paleozoic age has been established by inclusions of limestone found in outcrops north of El Tiro. The next event was the intrusion of a large stock of dacite porphyry into Paleozoic sediments and alaskite. The stock was some 3 miles wide and at least 6 miles long in a northwesterly direction. It was sharply confined along its southwest side by the major structure line. A number of large pendants of moderately folded Paleozoic sediments occur within and along its southwest edge. Thus the inferred, original major fault between Paleozoic and Cretaceous sediments became a contact between alaskite and Paleozoic sediments and then a contact between dacite porphyry and alaskite. Andesite porphyry may have been intruded later than the dacite porphyry, but relationships are not clear; it may be simply a facies of the latter. The intrusive activity was at this stage interrupted by an interval of erosion. The erosion surface probably was rugged, as there were local accumulations of coarse, angular conglomerate. Subsequently a series of volcanic flows and pyroclastics several thousand feet thick was deposited. A similar unconformity has been recognized elsewhere in the Southwest, particularly in the Patagonia Mountains near the Flux mine some 75 miles southeasterly. Here, as at Silver Bell, volcanics were deposited on an erosion surface cut in Cretaceous and older sediments which had been intruded by alaskite. Though no evidence is offered that closely defines the age of this unconformity, and proper analysis of the problem is beyond the scope of this paper, it is

Jan 1, 1955

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3'4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By R. Vogt, H. C. Mult, F. L. Wilke

INTRODUCTION At present, the capability of production planning software based on Linear Programming (LP) is still limited to the optimization of the single LP-run. This is due to the LP-model itself which cannot consider the interdependencies between individual LP- runs. With regard to planning of selective mining this limited way of optimization frequently leads to situations, where the remaining and accessible ore blocks do no longer allow to produce ROM-ore in the qualitative composition required by the ore processing plant. However, many of the aspects taken into consideration when setting up production plans built from mutually dependent LP-runs cannot be modelled in a system of linear equations. They are thus unsuited for treatment with LP and have to be taken care of by the planning engineer without any assistance by the system. The KBS currently under development is intended to assist the planning engineer in designing a production plan under special consideration of the combination of consecutive LP-runs and blending beds. It is not necessarily intended to find the optimum solution within a given planning situation which is, anyway, hard to determine due to the multitude of influences. The objective is rather to work out a good and - from the practical point of view - feasible production plan. The new aspect with respect to mine planning is the integration of expert knowledge and experiences via the KBS into the planning process in order to support the planning engineer. The planning system is being developed in close cooperation with an iron-ore open pit mine. COMPONENTS OF THE PLANNING SYSTEM The software is being developed on a workstation under UNIX and comprises the components LP, CAD-module and the KBS. The applied multi-goal LP-algorithm is an in-house development of the Department of Mining Engineering at Technical University Berlin. It was already successfully implemented within other mine planning programmes and was only slightly adapted to the specific needs of the present system. Within individual LP- runs it finds the optimum qualitative composition of ore production in the sense of the selected optimizing criterion and under the given restrictions: i.e. it determines tonnages to be mined from blocks in order to optimally meet the requirements of the ore pro- cessing plant. A CAD-module based on the commercial SURPAC package in combination with a simulation device is used to graphically depict the block model and progress of mining. Both LP-algorithm and CAD-package are integrated in the KBS. It has been decided to use the shell NEXPERT OBJECT as it is a hybrid system which supports both rule-based and object-oriented knowledge representation. MINE-MODEL AND LP-MODEL KBS have to be tailor-made for specific planning problems. Therefore, it had to be decided which specifications of the iron-ore mine should be represented in the model. As the limited possibilities of a university institute do not allow to develop a KBS for mine planning which is ready to use in industry, it was decided to concentrate on those characteristics that can be regarded as typical for iron-ore surface mines and that seemed to be suited for treatment with knowledge-based techniques. The following chapter summarizes the most important features of the mine model. The description of the requirements to the mine's sales products is followed by an outline of the applied LP-model. Mine model • The model of the mine as it is used for planning consists of • the block model of the deposit, • the mobile equipment, • stockpiles and blending bed and • the requirements to the sales products. The deposit is described by a block model which contains data on the chemical composition, LOI, grain size and tonnages. Grain size was included as it is important for the two sales products of the mine. Furthermore, it is known whichs blocks require and which don't require blasting; this is relevant to the assignment of loading equipment to individual blocks. The blocks are devided in three categories: • ore, which will directly be taken to the blending bed; • waste, which will be put on the waste dump; and • blocks which will be either transported to the blending bed, to stockpiles or to the waste dump depending on the specific planning situation. This decision is made during planning. Neighboring blocks are combined in mining areas to which the loading equipment is individually assigned. Mobile equipment comprises shovels and wheel-loaders as well as trucks. The characteristics of the loading equipment are important for their ability to load different blocks and for the permissible degree of their re-positioning etc. The mine disposes of a blending bed for homogenization of the production, of a waste dump, and of several stockpiles with different ore qualities. The requirement to make only limited use of the stockpiles for economic reasons is included in the KBS. According to long term planning two commercial products have to be produced, which differ both in grain size and qualitative composition (TABLE 1). Their mass-proportions in the blending bed have to be within a fixed range. Not considered in long term planning is the occasional need for lump ore, which occurs at very short notice and has to be produced in a "campaign-like" manner. This requires the total re-arrangement of all plans for on- coming blending beds and would therefore be ideally suited for

Jan 1, 1996

By W. W. Vaughn, R. H. Barnett, E. E. Wilson

Soon after the search for uranium ores on the Colorado Plateau began in earnest, thousands of feet of drill core ranging from 1 1/8 to 2 1/8 in. diam became available for study. Although significant advances had been made in the technique of quantitative gamma-ray borehole logging, instrumentation was in the development stage, and complete reliance could not be placed on gamma-ray logs alone to interpret quantitatively the meaning of radioactivity in a drillhole. A method that would be faster than chemical analysis and still give reproducible and reliable results for various drill core sizes was desirable to provide additional information on the enormous footage of drill core being accumulated. A solid phosphor scintillation drill core scanner was designed and constructed. Basically the instrument was developed to measure radiation from a drill core which would not be clearly recorded by a gamma-ray logger using a Geiger tube as the sensitive element. Such data would be beneficial in constructing isorad maps to delineate ore-bearing zones. A calibration in the range 0.01 to 0.1 pct eU.,O, was provided; above 0.1 pct eU3O8 gamma-ray logs were available and were being used to calculate grade and tonnage of ore reserves. The core scanner, however, has been used to estimate equivalent uranium content of ore-grade materials containing as much as 2.2 pct eU3O8 with an accuracy of ± 10 pct, the sample being in the form of a BX drill core. Actually, an apparent calibration of eU3O8 vs counts per unit time is a straight line with a slope that is a function of the sensitive element and the geometry of the counting assembly. A true calibration that will show the expected departure from a straight line is due principally to the random nature of the pulse from a radiation source and the nonlinearity of the electron circuitry. Design and Construction: Three methods of detecting radioactivity were considered and applied in developing the core scanner now in use: 1) the Geiger tube, 2) liquid scintillation phosphors, and 3) solid scintillation phosphors. The desired sensitivity and long-term drift characteristics needed for this operation could be attained only by using solid scintillation phosphors. All three methods are discussed. Before scintillation counters were common, nine beta-gamma sensitive Geiger tubes 7/8 in. diam by 12 in. long were used, arranged to surround the drill core with tube axes parallel to the axis of the core. This arrangement of Geiger tubes was en- closed in a lead shield 1 in. thick, and provision was made to slide a 6-ft length of drill core manually into the counting chamber, one foot at a time. A count for each segment was taken with a scaler while the core remained stationary. The equivalent uranium content of the different sections of drill core could then be estimated with the aid of a calibration curve of counts per unit time vs percent equivalent uranium (eU). In rare cases the effects of the radioactivity concentrated in small areas within the core introduced errors in the readings made with the Geiger tube arrangement owing to the geometry of the measurement. The variability of counting rate due to a localized concentration of radioactivity in a spot in the wall of a drill core is illustrated in Fig. 1. This effect and the inherent low efficiency of the Geiger tube were considered major disadvantages of this counting arrangement. When liquid scintillation phosphors became available the core scanner in Fig. 2 was constructed to make a more accurate measurement of the equivalent uranium content of a sample. This instrument contains about 4 liters of liquid phosphor in a stainless steel coaxial cylinder 1 ft long, with inner and outer walls 0.060 in. and 0.125 in. thick, respectively. Four end-window type photomulti-plier tube with cathodes of 2 in. diam, immersed in the solution at right angles to the axis of the core, were used to observe light flashes in the phosphor. The liquid phosphor offered equal sensitivity to radiation originating at any point in the enclosure and represented geometrically the optimum in design. However, providing a semi-permanent leak-proof seal between the glass envelope of the phototube and the metal walls of the container proved to be a serious problem in constructing the equipment. The most effective seals were especially machined O-rings from sections of large tygon tubing. The tygon took a permanent set owing to cold flow characteristics and in most cases sealed completely. The light absorption characteristics of the liquid phosphor changed gradually with time, and after one month the counting rate had decreased to half the original value. The most sensitive liquid phosphor tested proved to be a solution containing 4 g of 2.5-diphenyloxazole and 0.01 g of 2-(1-naphthy1)-5-phenyloxazole per liter of toluene. With fresh solution in the chamber and with all photomultiplier tubes operating in parallel, the counting rate contributed by any one of the four photomultiplier tubes was about 85 pct of the counting rate from a single tube operated individually. From these observations it was concluded that owing to coincident loss and light attenuation within the liquid phosphor, the apparent sensitivity could not have been materially increased by additional phototubes. However, this approach to core

Jan 1, 1960

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By K. W. Nelson, John N. Abersold

INDUSTRIAL hygiene has been defined by Patty' as "the science and art of recognizing, evaluating, and controlling potentially harmful factors in the industrial environment." This definition implies thorough study of operations, evaluation of potentially harmful factors through air sampling, micro-analyses and other means and finally, appropriate medical and engineering control wherever indicated. The prevention of industrial health injuries is a vital part of operations of American industry today. Progress and interest in this field has increased steadily for many years, the most rapid progress having been attained, perhaps, during the last three decades. It is significant to note that there are now official agencies in 46 states actively concerned with industrial health problems and that a western field station has been established recently in Salt Lake City by the U. S. Public Health Service to augment its industrial hygiene services directed from headquarters of the National Institute of Health, Bethesda, Md. Many of the larger industries have found it advantageous to establish their own industrial hygiene departments. The American Smelting and Refining Co. is a world-wide organization engaged in the mining, smelting, and refining of lead, copper, zinc, silver, gold, by-product metals, including cadmium, arsenic, and others. In the United States there are 13 smelters and refineries, 11 secondary smelters or foundries, and a number of mines. Approximately 9000 workers are normally employed. It has long been the established company policy to seek out occupational hazards and provide safeguards for employee health. Protective equipment has been supplied to individual workers and exhaust ventilation installations have been in use in some operations for more than 40 years. All of the major units have their own medical departments which provide employees with excellent medical and hospital care. In 1937 full scale industrial hygiene studies were undertaken at the Selby Plant and were extended to most of the other smelters during the next three years. In 1945 the Department of Hygiene was organized with Professor Philip Drinker of Harvard University as Director and with Dr. S. S. Pinto as Medical Director. The department is responsible for coordinating and maintaining a program for the good health of all employees from top management down to the lowest paid day worker. It is essentially a service organization serving all of the United States plants regardless of location or size. Full and part-time physicians employed in all of the company's American plants and working in close cooperation with the Medical Director are responsible for de- termining the state of health of all the employees and giving treatment when necessary. In general, medical care is confined to accidents or illnesses occurring while the men are on the job. Among the duties of the doctors is the making of careful physical examinations of new employees and routine check-ups of old employees. In addition to medical care a primary responsibility of the department is the prevention of occupational illnesses. In this the main concern is with the working environment in relation to its effect on the worker. Environmental factors may be dusts, fumes, gases, toxic materials, heat, humidity, radiation, or noise. The objectives are: (1) Immediate control of these factors through the education of the worker, through providing the wearing of respirators or other protective devices, and through careful medical examinations and regular analysis of urine specimens; (2) a long range control program which may be accomplished by local exhaust ventilation, wetting of materials, changes in metallurgy, changes in methods of handling, or by use of special devices and special equipment. To accomplish these objectives a fine industrial hygiene laboratory was built in Salt Lake City and equipped to do routine and experimental work. Trained and experienced industrial hygienists obtain the facts by making frequent hygiene surveys. These surveys include tests of the air, studies of all processes, and careful investigation of ventilation, lighting, and general working conditions. Except in emergencies, the air contaminants and often the substances handled by the worker are sent to the laboratory for analysis by chemists and technicians specially trained in industrial hygiene methods. The findings are evaluated in terms of limits recommended by various State and Federal agencies, and in light of all available medical data. The methods used for studying the working environment involve all of the usual chemical and physical procedures employed in industrial hygiene. The Impinger, electric precipitator, thermal pre-cipitator, and filter paper sampler have been used to collect atmospheric dust and fume samples. Of special interest here is the filter paper sampler, shown in Fig. 1, which was developed by Dr. Silver-man at Harvard University. The instrument has been improved and is used very extensively in field studies. A water manometer connected behind an orifice is used to determine the rate of air flow. Calibration is effected by use of a standard gas meter or rotameter. The dust or fume is collected on a filter paper clamped between two rings, as shown in Fig. 2. The filter paper, such as Whatman No. 52, collects both dust and fume with a very high efficiency. The instrument is very convenient and easily transported. The solids collected on the filter paper are analyzed in the laboratory usually by use of a polar-ographic procedure. By this procedure it is possible to measure quantitatively in a single analysis the

Jan 1, 1952

By A. E. Lillstrom

IN the development of iron mines and production of iron ore from the Marquette range, drilling blast-holes is an important phase of the mining cycle. The ground drilled in ore production can be classified into two main categories, soft hematite and hard hematite or magnetite. Within these categories the material exhibits a wide range of penetrability by percussion drills. Development work encounters various types of rock. Slate and altered basic intrusives constitute the softer types commonly encountered. Harder materials are represented mainly by greywacke, quartzite, iron formation, and diorite. Prior to the first tungsten carbide trials in late 1947 and early 1948, hard-rock and ore drilling was done with steel jackbits starting at 21/4-in. diam. These were reconditioned by hot milling. Automatic or handcrank 31/2-in. drifters were employed, mounted on Jumbos, posts and arms, or tripods, depending upon the working place. With the exception of shaft sinking jobs where 55-lb sinker machines were and still are used with 1-in. quarter octagon steel, the other production and development mining utilized 11/4-in. round and Leyner-lugged steel. The following properties have been selected as typical examples wherein carbide bit applications have proved economical. The Mather mine "A" and "B" shafts and Cleveland-Cliffs Iron Co. mines are soft ore mines where insert bits are used in rock development only. The Greenwood mine, Inland Steel Co., Champion mine, North Range Mining Co., and Cliffs shaft mine, Cleveland-Cliffs Iron Co., are hard ore mines where all drilling is done with tungsten carbide bits. Mother Mine "A" Shaft In the Mather mine "A" shaft and other soft ore properties where only rock development work is done with the tungsten carbide bits, several types and makes of bits have been tried since early 1948. The greatest proportion of failures have been at the connection end, although the early trials with the 13 Series Carset 11/2-in. bit used in conjunction with 31/2 -in. automatic-feed drifters, showed an equal amount of shattered inserts. To combat this shattering, the 31/2 -in. drifters were replaced by 3-in. drifters, thus eliminating, for the most part, insert failures. However, the attachment end of the rod continued to be the main source of trouble. The greatest amount of failure was in the stud or at the upset section approximately 2 in. behind the drive shoulder of the rod. Heat treatment was changed several times as well as the composition of the alloy studs. Since this failed to correct the trouble, a decision was made to change to a heavier attachment section. Timken 11/2-in., type M, bits were then employed and showed an exceptional improvement. The rods are discarded when the thread contour shows sharpening or wear on the shoulder. It was also learned that the Timken insert did not show as rapid gage and cutting edge wear as did competitive makes, and footage per use increased by approximately 50 pct. Prior to the Timken trials the average life per bit at the Mather mine "A" shaft on 6-ft change chain-feed drifters was 500 ft, and the rod life at the connection end was 50 ft. The Timken bit with chrome-plated thread averaged 1200 ft, and rod life increased to as much as 500 ft. However, the life of the connection end was much better on shorter length drill rods or in places where machines with 34-in. change were used. The bit thread continued to be the point of ultimate failure with thread strippage, constituting the cause for discard of bits. In one of the new development headings, harder rock was encountered for approximately 800 ft, dropping the life per bit to a low of 90 ft with shank and thread life of rods dropping to approximately 125 ft average. The stripped bits were then welded to the rods, increasing the life per bit by 75 to 100 pct. The rod transportation for main level development was not a problem so intraset rods were tried. Intraset rods have tungsten carbide inserts set into the rods proper by the manufacturer and can be obtained with chisel or four point bits. This type of rod eliminates the need for any connection and the steel being a special alloy will show more feet drilled per rod. The first trial was made with eight rods, and final results averaged 350 ft per rod, six of the rods worked the life of the bit end, and two broke shanks at less than 50 ft. The preceding example showed a considerable improvement, so additional steel of the same type was purchased, but its use has been limited to main level drifting only, because of the handling problem involved in transportation of the complete rod to mine shops for resharpening. Further trials are being made on improving the life per detachable bit by chrome plating. To date, the chrome plating shows an improvement of approximately 100 pct. However, final results will not be known until the present long term trials have been completed. Mother Mine "B" Shaft In November 1947, tungsten carbide bits were first tried at the Mather mine "B" shaft. The use of 1%-in. Carset 13 Series bits, for drilling the 72-hole, 7-ft shaft round, decreased the drilling time from an average of 41/2 hr per round required with steel bits, to 2 hr with insert bits. The best drilling time for

Jan 1, 1952

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman' have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By David L. Holt, Walter A. Backofen, Anwar-uI Karim

Specimens of a hydrided Mg-0.5 Zr alloy were strained in tension at 500°C and constant rates of 2 x10-3 5 x 10-3, and 2 X 10" min-1. Hydride-denuded zones formed at grain boundaries normal to the tensile-stress direction as a result of magnesium transport during difusional flow. The width of the zones could be measured and the measurement used for calculating the diffusional component of the imposed tensile strain. The strain from diffusional flow was found to increase with imposed strain at a diminishing rate, tending to saturate at approximately 12 pct. Strain rate sensitivity of flow stress was low. The apparent non Newtonian character of the diffusional flow is attributed to a non Newtonian process acting in parallel with it which could be boundary shear. Fracture grows out of voids that form in the denuded zones. DEFORMATION of a grain by diffusion of atoms from boundaries stressed in compression to boundaries stressed in tension is Newtonian viscous,1-3 and evidence has accumulated in recent years that such a process may be responsible for the high strain-rate sensitivity of the flow stress of super-plastic alloys.4"7 One piece of evidence is that experimental stress: strain-rate relationships can be quantitatively explained.5-7 There is also metallo-graphic evidence of diffusional flow in superplas-ticity, but in a limited amount. The formation of striated bands on the surface of superplastically deformed specimens has been attributed to diffusional flow.5"7 The basis of that attribution came from experiments on a coarse-grained, nonsuperplastic and hydrided Mg-½ wt pct Zr alloy which formed hydride-denuded, light etching zones at tension-stressed boundaries when strained in tension at 270?C.6 The origin of these zones had already been traced to the diffusional flow of magnesium atoms to the boundaries.' The particular observations in the more recent work were of striated-band formation on the surface and denuded-zone formation internally, with both the bands and zones having the same width and appearing at tension-stressed boundaries. It was argued that the bands were a surface manifestation of the zones and hence of diffusional flow. Of course in superplastic alloys which do not contain internal metallographic "markers", the surface bands can be the only metallographic indication. In the present work, denuded-zone formation was utilized, as it has been by others,9-11 to extend the observations of diffusional flow and to measure the strain, ed, resulting from it. Grain size had to be large to measure ed with accuracy. The grain size chosen for this study was -30 , and with that a strain of 10 pct from diffusional flow produces a denuded zone only 3 µ in width. The large grain size naturally precludes superplasticity. The observations of diffusional flow were complemented by determining the strain from the other operative deformation modes: slip, e,, and grain boundary shear, egb. An incremental specimen extension is the sum of increments from slip, and grain boundary shear as well as diffusional flow. Division by a common length is required to convert to strain. If this length is taken as the initial specimen length, then imposed engineering strain, e, is given in terms of the component engineering strains by e = ed + es + egb [1] Stress:strain-rate relationships are determined by the way in which this "strain balance" is made up. EXPERIMENTAL Material. Zirconium hydride markers were introduced into the Mg-0.5Zr alloy by annealing in hydrogen at 450°C for 30 min. The hydride concentration was particularly high at zirconium rich stringers, which was fortunate in that the transverse boundaries at which denuded zones form lie perpendicular to the stringers. Grain size after annealing was 30 µ. Photomicrographs of unstrained and strained material are shown in Fig. 1. Procedure. Specimens were strained in tension with an Instron machine at crosshead velocities of either 2 x 10"3, 5 x X or 1 x 10-2 in. min-'. Specimen length and diameter were 1.0 and 0.2 in., respectively, so that initial strain rates in tests at constant crosshead speed were 2 x 10"3, 5 x X and 1 X l0-2 min-1. Tests were made at 500°C which is a compromise temperature at which diffusional flow is still measurable but grain growth is not active enough to interfere with metallographic measurements. The tests were made in a hydrogen atmosphere. Strain Balance. An equation additional to [I] is eg = ed + es [2] where eg is strain measured from grain elongation. Measurement was made of ed, eg, and, of course, e, which enabled all the strains in Eq. [I] to be determined. For this purpose, strained specimens were sectioned longitudinally, polished, and etched. The strain from diffusional flow, ed, was computed by measuring on photomicrographs the width in the tensile direction of denuded zones at either end of a grain XI, X2, adding them, and dividing by twice the initial longitudinal grain dimension L0, Fig. 2. Reported values are the results of measurements on seventy randomly selected grains; 95 pct confidence limits on ed were +1.5 pct strain. To measure eg, the maximum length, L, and the maximum width, W,

Jan 1, 1970

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 T. E. Evans, C. T. Baroch

ZrB2 was produced in batches of 4 to 6 Ib by interaction of ZrO2, B4C, B203, and carbon at around 2000°C in a simple graphite resistance furnace. Techniques of production are discussed and the final design of a suitable furnace is described in detail. Several other borides were made by the same technique and the process appears to have possibilities for commercial production. N seeking out new hard and refractory com- pounds, many researchers have turned to the investigation of the borides and excellent papers have been published on the properties of these compounds. Few papers, however, have appeared on the techniques and problems concerned with the production of these high temperature substances. This report describes progress made in developing a method for preparing zirconium diboride, ZrB2, on a pilot plant scale. The literature of the borides and other refractory hard metals recently has been reviewed, annotated, and classified so completely' that it is needless to attempt such an outline here. It is enough to say that three borides of zirconium have been reported: ZrB, ZrB2, and ZrB12.2 ZrB2 is the most stable of these and is especially stable in the presence of carbon up to and including its melting point of around 3000°C. Like most borides, it can be prepared in several ways. It can be prepared by synthesis of the elements, but these are expensive and difficult to produce in a high state of purity. Obviously, production directly from the oxides would have decided economic advantages. In electrolytic production such as that of calcium boride,:' the product is recovered as a sludge mixed with electrolyte; and separation of product from adhering electrolyte and regeneration of the electrolyte is an involved and difficult process. The work on borides was started on a small scale in 1948. Late in 1949, Naval Ordnance expressed a specific interest in ZrB2 and the project then centered on this compound. After the usual experimental work necessary in a new field, ZrB2 of good quality was produced by heating mixtures of B4C, ZrO2, B2O3, and carbon to a temperature of about 2000 °C in a resistance-type electric furnace. Over 100 lb was made for experimental use tests, and the method of production probably could be expanded into a commercial operation. A similar process has been described by Kieffer and coworkers.' The main chemical problems were the development of proper charges to insure complete reduction of the elements, determination of the proper temperature range at which these reductions took place, and adoption of techniques necessary to pre- vent inclusion of such impurities as carbon and nitrides. The mechanical problems consisted of developing a simple practical furnace that would attain the high temperatures required and permit use of a controlled atmosphere when necessary and determining of suitable refractories. Both problems were solved by designing a crucible resistance furnace. Crucible Resistance Electric Furnace Attempts were first made to produce ZrB2 in an electric arc furnace, but such a furnace would not provide the degree of carbon control required for producing clean graphite-free borides, so it was decided to try working in a crucible. Obviously, the furnace would have to be constructed of graphite, as the temperatures required are too high for other refractories or heating elements. Crucibles were made by hollowing out segments of graphite electrodes, which were fitted with a cover and clamped between two electrodes so that the current passing through the thin wall of the crucible would generate heat, using the principle of the Helberger crucible furnace."? Preliminary tests with this type of furnace were encouraging and led to the furnace design shown in Fig. 1. The essential components were a thin-walled graphite crucible resting on a graphite block, which formed the lower electrode assembly, and a top electrode assembly swung from a pipe column making contact with the top of the crucible. The space around the crucible was filled with graphite prepared from waste electrodes crushed to about ¼ in. This packing had excellent insulating properties, both electrically and thermally, and could be removed easily and quickly from around the crucible by means of an industrial vacuum cleaner. The largest resistor crucibles were machined from 8 in. electrode stock and were 26 in. long, with a side wall Yi in. thick and a 1 in. bottom. Temperatures were determined optically by sighting down a 1 in. hole drilled longitudinally through the top electrode and the crucible cover. Sealing this hole at the top was a water-cooled brass sight-glass assembly, shown in Fig. 2. An opening was provided for a light flow of helium to keep the sight opening clear of smoke, and a glass prism above the sight glass changed the line of sight to the horizontal for easier reading. More recently, the prism and optical pyrometer were replaced by a photoelectric recording pyrometer. At first the charges were placed directly in the resistor crucible but this meant that everything had to be withdrawn from the furnace every time the charge was emptied. Later, smaller crucibles were made up that could be placed inside the resistor

Jan 1, 1956

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By Niels Hansen

The substructure formed by drawing at room temperature in aluminum (99.5 and 99.998 pct purity) and in recrystallized aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum -oxide was examined by transmission electron microscopy, and the flow stress of the drawn materials was measured by tensile testing at room temperature. A sub-grain structure was present after a reduction in area by drawing of 10 to 20 pct, and the subgrain size was observed to decrease with increasing deformation. The tensile data show that the increase in flow stress (0.2 pct offset) by drawing from 10 to 95 pct depends on the reduction in area, not on the composition of the materials. Dispersion strengthening and subgrain bowzdary strengtlzening contribute to the flow stress, and these strengthening processes have been found to be linearly additive. The flow stress (0) can be related to the subgrain size &) by the Petclz relation = uo + k . t, where go is dependent on the composition of the products and k is approximately the same far all materials. THE microstructure of dispersion-strengthened aluminum aluminum-oxide products consists of small oxide plates distributed in an aluminum matrix. The matrix structure depends on the manufacturing history, and in hot-worked as well as cold-worked products the matrix is divided by subgrain (or dislocation) boundaries. For hot-extruded products it has been shown1 that dispersion strengthening and subgrain boundary strengthening are linearly additive, and the flow stress (0.2 pct offset.) at room temperature has been related to the subgrain size (ts) by a Petch equation,2,3 s = so + k . ts-1/2, where s0, increases with increasing oxide content. For cold-worked products containing subgrains no systematic work has been reported, and it was the aim of the present study to examine the microstructure and the relationship between the flow stress and the subgrain size for such products. The behavior of' aluminum aluminum-oxide products depends on the purity of the aluminum matrix, and aluminum of the matrix purity (99.5 pct) was included in the investigation. The literature contains few data about the behavior of this impure aluminum, and aluminum of a higher purity (99.998 pct) was therefore also examined. As regards the relationship between the flow stress and the subgrain size in cold-worked dispersion-strengthened products, no systematic work has been reported. For aged cold-worked structures containing fine precipitates (Fe-Mo carbide) a Petch relation has been found,4 and it has been shown that the k value NlELS HANSEN is Head, Metallurgy Department, Danish Atomic Energy Commission, Research Establishment Riso, Denmark. Manuscriot submitted January 9, 1969. IMD is approximately the same as in iron, whereas the s0 value is higher owing to the presence of the precipi-tates. Investigations of metals such as tungsten,' ferrous metals,4,6 and molybdenum7 cold drawn or swaged at room temperature have shown that the flow stress can be related to the subgrain size by a Petch relation when ts is taken as the subgrain size perpendicular to the direction of deformation. For aluminum no work has been reported on the relationship between the flow stress and the subgrain size after deformation at room temperature, whereas for aluminum tensile strained at different temperatures in the range -183" to 375°C a Petch relation has been found by taking ts equal to the subgrain size.' In the present study two aluminum materials (99.998 and 99.5 pct) and three aluminum aluminum-oxide products (containing 0.2, 1.0, and 4.7 wt pct oxide) were drawn at room temperature to reductions in area from about 10 to about 95 pct. The structures were studied by transmission electron microscopy, and the flow stress (0.2 pct offset) was measured at room temperature. EXPERIMENTAL Materials. The materials are given in Table I together with the chemical analysis. The three aluminum aluminum-oxide products were manufactured from aluminum powder that had been compacted and Table I. Chemical Analysis of Materials Al203 Fe SI Material wt pct wt pct wt pct 99.998 pct* - 0.0004 0.0012 Aluminum 99.5 pctt - 0.36 0.16 Aluminum AlMD13† 0.2 0.16 0.12 Aluminum- -Oxide AlMD105† 1.0 0.26 0.18 Products SAPISML960s† 4.7 0.22 0.19 *Other impurities: O.0004 pct max each of Cu and Zn (supplier's analysis). †Other impurities: 0.03 pct max Cu. 0.02 pct max each of Mn, Mg, Zn, Ti. Table 11. Mean Diameter of Aluminum-Oxide Particles in Extruded and in Cold--Drawn Aluminum Aluminum-Oxide Products Mean Diam. of A1203-Plates* Material State A AlMD105 Extruded 540 Cold Drawn 97 pct 510 SAP ISML 960 Extruded 770 Cold Drawn 95 pct 820 *The standard deviation of the mean is approx. 5 ±pct.

Jan 1, 1970

By R. H. Jamison

A relatively new haulage system is described. Employed by the Delmant Fuel Co.. the "Full Dimension" system provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. This system is said to provide a higher percentage of recovery as well as additional safety and production. Delmont Fuel Co. is employing a comparatively new system of transportation known as a Full Dimension system. Cne of these systems has been in operation for a year at the company's 10-B Mine as a part of a conventional section. A second was installed at the No. 10 mine in late 1960 to handle the production of a Colmol in a pillar section. SYSTEM COMPONENTS A Full Dimension system is a haulage system that provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. The equipment required for this system consists of a series of interconnected chain conveyors that are mobile and articulated. They will retract or extend a sufficient distance for the development of a five-entry system; or, in the Colmol pillar section, it provides reach of 210 ft in all directions from the section belt. The components of this system are: l)One 160-ft chain line placed in tandem with the belt conveyor. It has a self-propelled drive, is 20 in. wide and 9 in. deep. Moving this conveyor requires the assistance of a loading machine or cutting machine. 2) One 40-ft piggyback that discharges along the entire length of the 160 ft chain conveyor. 3) A mobile bridge carrier, which is a self-propelled conveyor with four wheel steer and four wheel drive, twenty-eight feet long, it delivers coal to the receiving end of the piggyback. Axles steer individually making possible almost lateral movement. 4) Another 40-ft piggyback, duplicate of item 2 that delivers coal along the entire length of item 3 (mobile bridge carrier). 5) A second mobile bridge carrier, similar to the first, which deliver coal to the piggyback (item 4). 6) A third 40-ft piggyback, duplicate of items 2 and 4. This pig is attached to the loading machine and delivers its coal along the length of the second mobile bridge conveyor. Since the original preparation of this paper, the Delmot Fuel Co. has been able to eliminate the 160-ft chain conveyor. This was accomplished by connecting the outby piggyback directly to a loading machine with an extended boom. The loading machine loads directly onto the belt. This change has resulted in a substantial reduction in moving time and greatly increased flexability. A single trailing cable powers the entire string of equipment. It is attached to the side of the equipment in such a way as to keep it off the ground and afford maximum protection. The tramming rate of this equipment is 90 fpm. The conveyor capacity in a conventional section at Delmont's mines is 7.5 tpm and in the Colmol section is 5.5 tpm. This regulation is a simple function of conveyor speed. To visualize operation of this equipment, it would be well for me to touch briefly on local conditions in the Upper Freeport seam in which we mine. (Also, see the photographs of some of the equipment in use.) DELMONT'S TOPOGRAPHY The Delmont Fuel Co. operates two mines in this seam in Westmoreland County, Pa. The No. 10 mine, which was opened in about 1912, is now almost worked out. Depending on economics in the industry, it has a life of two to four years on a declining production basis. A year ago a new drift mine was opened which is called No. 10-B. It is about two miles from the cleaning plant and is connected thereto by an overland belt conveyor. The new mine is being developed at a rate calculated to take up the slack as the old mine plays out. The Upper Freeport seam averages 4.2 ft in thickness in the area of the Delmont mines. It carries 4 in. of boney coal at the top of the seam and a middle man of from 2 to 4 in. We mine just above a 1-in. slate parting which has 4 to 6 in. of highly laminated coal beneath it. This material normally makes a very firm bottom. The roof varies from dark shale to sand rock and 36-in. bolts are placed on 4-ft centers for roof support. All working places are driven 20 ft wide on development and 25 ft wide on retreat. Selection of mobile chain conveyor equipment when it became available, was a very natural move for Delmont Fuel to make, because chain conveyors and piggybacks had been in use at the company's mines for about 12 years. Grades in the new mine

Jan 1, 1961

By Brian F. Dyson

The surface tensions at 1550°C of some Fe-S alloys (in the range 0.008 to 0.052 wt pct S), Fe-Sn alloys (0.31 to 48.4 wt pct Sn), Fe-P alloys (0.038 to 2.38 wt pct P), Fe-Cu alloys (2.15 to 22.8 wt pct Cu), and Fe-1 pct C-S alloys (0.005 to 0.076 wt pct S) along with the surface tension of the base iron have been measured by the sessile-drop method. A mean value of 1754 dynes per cm was found for the surface tension of the base iron. Sulfur was found to be highly surface-active, the surface-tension results being in quantitative agreement with existing data. Tin and copper were found to be less surface-active than sulfur while phosphoms was completely nonsurface-active. The surface tensions of Fe-1 pct C-S alloys were found to be lower than those of the Fe-S alloys containing the same sulfur content. This was shown to be a mmzifestation of the increase in the thermodynamic activity of suZfur by carbon. It is only in recent years that attempts have been made to measure the surface tension of liquid iron of known high purity.1-3 Earlier measurements4-7 were made on liquid iron containing variable amounts of what are now known to be surface -active solutes. The exact value of the surface tension of liquid iron is still, however, open to some doubt. Halden and Kingery' reported a value of 1720k 34 dynes per cm at 1570°C, Kozakevitch and Urbain8 gave 1790k 25 dynes per cm at 1550°C, while Van-Tszin-Tan et al. obtained a value of 1865k 37 dynes per cm at 1550°C. The first systematic investigation into the effect of controlled solute additions on the surface tension of iron was made by Halden and Kingery.' They showed that sulfur and oxygen were highly surface-active, whereas nitrogen was only slightly active, and carbon inactive. A subsequent investigation by Kingery indicated that two other group-6B elements, selenium and tellurium, were also surface-active. This highly surface-active nature of sulfur and oxygen has recently been substantiated by Kozakevitch and Urbainla and Van-Tszin-Tan et al. l1 Kozakevitch and Urbainl2 have also conducted an experimental survey of the effects of a number of metals on the surface tension of liquid iron. Their surface-active nature was, in all cases, less than that of the group 6B elements. The present investigation was undertaken to study in more detail the surface tensions of dilute Fe-S alloys and to measure the surface tensions of binary alloys of iron containing phosphorus, copper, and tin. The effect of sulfur additions on the surface tension of Fe-1 pct C alloys was also determined. EXPERIMENTAL PROCEDURE The sessile-drop method was employed in the present investigation. An apparatus was built similar in principle to that described by Humenik and Kingery.lS It consisted of a horizontal silica tube, which could be evacuated to pressures less than 10-5 torr, with its central portion surrounded by a water jacket within which was a high-frequency coil. This generated heat in a tantalum susceptor placed inside the silica tube, which in turn radiated heat to the specimen mounted on a recrystallized alumina plaque. Temperatures were measured by an optical pyrometer and photographs of the molten drop were taken on a fixed-focus plate camera giving a magnification of X2. Surface-tension values were determined from the resultant drop using the method described by Baes and Kellogg.l4 The high vapor pressure of molten iron made it necessary to conduct all the experiments under a 1/4 atm of argon (greater than 99.995 pct purity). The analysis of the base iron used in the investigation is given in Table I. Each sample was approximately 3 g in weight and had a hemispherical base to ensure a uniform advancing contact angle on melting. The iron alloys were prepared individually in the sessile-drop apparatus by drilling a hole in the top of each sample and adding the required amount of solute, the drops being analyzed after the experiment. This method of preparation had the advantage of ensuring a consistent minimal contamination by oxygen due to refractory attack and also allowed surface tension to be measured at the same time. Every precaution was taken to ensure that the specimen was not contaminated by grease when it was introduced into the apparatus, the samples being cleaned in acid, dried in alcohol, and rinsed in petroleum ether. All handling was done with tweezers. Once the specimen had been placed inside the susceptor, the furnace was evacuated and the Sample leveled. The furnace was then degassed at approximately 1000"C before the argon was introduced. In every case the surface tension was determined at 1550" C.

Jan 1, 1963

By W. W. Whitaker, C. W. Manry, R. H. McLean

In an eccentric annulus, cement may favor the widest side and bypass slower-moving mud in the narrowest side. Tendency of the cement to bypass mud is a function of the geometry of the annulus, the density and flow properties of the mud and cement and the rate of flow. Bypassing can be prevented if the pressure gradient protluced from circulation of the cement and buoyant forces exceeds the pressure gradient necessary to drive the mud through the narrowest side of the annulus at the same velocity as the cement. In the absence of buoyant forces, one requirement for this balance is maintenance of the yield strength of the cement greater than the yield strength of the mud multiplied by the maximum distance from the casing to the wall of the borehole and divided by the minimum distance. If the yield strength of the cement is below this value, bypassing of mud cannot be prevented unless buoyant forces or motion of the casing significantly aid the displacement. INTRODUCTION Successful primary cementing leaves no continuous channels of mud capable of flow during well treatment and production. Prevention of channels requires care. Tep-litz and Hassebroek provide evidence of channels of mud after primary cementing in the field.' Channeling of cement through mud in laboratory experiments has also been reported.'-' Recommendations for improving the displacement of mud include (1) centralizing the casing in the borehole,'-" 2) attaching centralizers and scratchers to the casing and moving it during displacement,18 "3) thinning the isolating the cement by plugs while it is circulated down the casing,%( (5 establishing turbulence in the cement," and (6) holding the cement slurry at least 2 lb/gal heavier than the mud and circulating the cement slurry at a very low rate of flow.' Although much has been written about the above parameters, the relative importance of each has not been well defined. In this investigation, the mechanics of mud displacement are described through results from analytical models and experiments. The model chosen — a single string of casing eccentric in a round, smooth-walled, impermeable borehole — is analagous to casing centralized in a borehole which is not round and to placing more than one string of casing in a borehole. In each, some paths for flow are more restricted than others. A fluid flowing in the borehole may seek the least restricted, or most open, path. This tendency for uneven flow can lead to channeling of cement through mud unless preventive measures are taken. The analytical models describe channeling and give means of balancing the flow. Experimental data test the analytical models and illustrate effects of motion of the casing, differences in density and mud's tendency to gel. Results are encouraging. Piston-like displacement of mud by an equal density cement slurry is possible through proper balance of the flow properties of the mud and cement slurries to the eccentricity of the annulus. The more eccentric the annulus, the thicker must be the cement relative to the mud. If proper balance is not achieved. bypassing of mud by cement cannot be prevented without assistance from motion of the casing or buoyant forces. Increasing the rate of flow can help to start all mud flowing but cannot prevent channeling of cement through slower moving mud in an eccentric annulus. Thinning the cement slurry tends to increase channeling although the extent of turbulence in the annulus may be increased. Description of flow in an eccentric annulus begins in the next section. It is assumed that (1) the casing is eccentric and is stationary, (2) the mud and cement slurries have the same density and (3) the gel structure of the mud has been broken and the mud and cement follow the Bingham flow model. Effects related to these restrictions will be discussed. FLOW PATTERNS SlNGLE FLUID IN ANNULUS Flow of a single fluid through an eccentric annulus is illustrated in Fig. 1. Part A shows laminar flow of a Newtonian fluid. This distribution of flow was calculated by Piercy, Hooper and Winney.' In fully developed turbulent flow, the velocity distribution around the annulus is less distorted, but the flow still favors the widest part of the annulus Parts B, C and D of Fig. 1 are a qualitative representation of the flow of a Bingham fluid. The yield strength of the fluid increases the severity of bypassing compared to Newtonian flow. At a very low rate of flow, all flow is confined to that portion of the annulus which has the minimum perimeter-to-area ratio. The fluid shears on the perimeter of that area when the pressure gradient multiplied by the area just exceeds the yield stress of the fluid multiplied by the perimeter. Whether or not the minimum perimeter-to-area region encompasses all of the annulus or only a part (as shown in Part B) depends on the geometry of the annulus. If only a part begins to flow, increasing the rate of flow increases the area flowing until finally there is flow throughout the annulus.

By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.'- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin' has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled' that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967