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By Gordon H. Geiger, John M. Svoboda

One mechanism of metal penetration into mold aggregates by cast steels is vapor state mass transport. In order to further understand and quantify this mechanism, the steady-state diffusion of metallic vapors was studied at 1250" to 1600°C in controlled oxygen pressure atmospheres by measuring the weight loss from a metal bath whose vapors were allowed to diffuse through a porous aggregate compact held at constant temperature. Mass transport rates substantially greater than those predicted from the assumption that the vaporizing species was the elemental metal vapor were observed. Vaporization rates were found to increase with an increase in the oxygen partial pressure in the gas atmosphere with maximum vaporization occurring at oxygen partial pressures just below those in equilibrium with a liquid oxide layer at the given temperature. When the liquid oxide layer was present, no vaporization was observed. Metal carbonyls were ruled out as the vapor species involved because of their thermodynamic properties. The species with the enhanced volatility were deduced to be gaseous metal-oxygen molecules, probably the polynuclear oxides (FeO)2 and (Mn0)2. Diffusion followed the ordinary diffusion mode, and Knudsen diffusion is not important in normal foundry molds. The interdiffusivities of the metallic vapors and the mold atmosphere, through the porous aggregates, were measured. The effective interdif-fusivity of the vapor species and mold atmosphere through the aggregate may be expressed as follows: Deff,12 - — where E is the void fraction of the aggregate and 7 is the "tortuosity factor". Aggregate material had no effect on diffusion rates, and the only relevant parameter was the void fraction. Values for 7 ranged from 3 to 6 for normal foundry aggregates with 4 being considered a good representative value. An area of interest in high-temperature metallurgical processes which has received little attention in the past is the diffusion of metal vapor species in porous aggregates. Research into the metal penetration phenomenon' in foundry molds has shown that a major penetration mechanism is the vapor transport of metallic species into the porous foundry sand molds, followed by condensation of metallic films on the sand grains. Considerable study of the vaporization of metallic species has been reported in the literature, and the vapor transport properties of many metallic species have been determined.2'3 Many instances have been observed where the vaporization behavior could only be explained by the existence of a metallic species with a vapor pressure greater than the elemental metallic species. These species were identified or, in some cases, presumed to be carbonyls,4,5 hydroxides,6-9 or vaporous oxides.10-16 The diffusion of gases through porous aggregates has received considerable attention in the literature pertaining to catalysis, although primarily at low temperature, and more recently in the literature concerned with ore reduction.17-22 The following experiments were devised and carried out in order to determine the nature of the metallic species involved in the metal penetration phenomenon, and the effective diffusivities involved. EXPERIMENTAL APPROACH Steady-state diffusion was selected for experimental convenience. The experimental systems used, shown in Figs. 1 and 2, consisted of a porous aggregate specimen contained in an impermeable alumina tube held above, and just separate from a metal bath. The entire system was held at constant temperature and pressure in a furnace with a controlled oxygen partial pressure atmosphere. After a brief period of nonsteady state behavior, a steady flux of metal vapor through the porous aggregate will develop due to the concentration gradient of metallic vapor in the gas phase. The flux of metallic vapor from pressure may be neglected because there is no pressure gradient. There is no flux from convection because there is no net flow of gas within the metal-aggregate system, and thermal diffusion is negligible compared to the flux from ordinary diffusion. If the material being studied is allowed to vaporize until steady-state behavior is attained, the experimental results may be analyzed using Fick's First Law.

Jan 1, 1970

By F. F. Skiba, J. E. Warren

An idealized miscible displacement process in a three-dimensional, heterogeneous porous medium has been studied via experimental computation based on a "Monte Carlo"' model. The macroscopic dispersion which results solely from variations in the permeability of the porous system is related to the scale of the heterogeneity as well as the distribution function for the permeabilities. The interpretation of laboratory data is often subjective and may bt? misleading since ambiguities are not always recognized. Furthermore, an experiment performed on a conventional oil-field core does not yield a valid measure of Macroscopic dispersion for reservoir engineering purposes since the scale of heterogeneity that is significant in the laboratory is not significant in the reservoir. The analysis of field-performance data is discussed and it is shown that a unique characterization of the reservoir can not be obtained from this information alone. A possible method based on a minimum of data, for estimating the spatial distribution of permeabilities in a reservoir is postulated INTRODUCTION Many studies concerned with diffusion and dispersion in porous media have been undertaken because of the potential importance of miscible displacement processes for increasing the recovery of oil. The results from a large number of these studies have been published; in a recent paper Perkins and Johnstonl presented a comprehensive survey of the pertinent literature and excellent appraisal of the "state of the art". In this investigation, dispersion resulting from macroscopic variations in the properties of the porous medium is of primary interest. Dispersion, in this sense, is caused by fluctuations in the velocities of the individual fluid elements as they move through the porous system. This phenomenon is the result of inhomogeneities in the permeability and/or porosity, but it can be amplified by differences in the characteristics of the fluids involved. The objectives of this study are the following: (1) to determine the qualitative manner in which macroscopic rock properties affect the observed dispersion coefficient; (2) to evaluate the possible influence of macroscopic dispersion on laboratory experiments; and (3) to appraise the significance of macroscopic dispersion with regard to reservoir performance. Investigations of this type are essential since many miscible displacement processes, while seemingly understood from a mechanistic point of view, do not behave in a predictable manner under field conditions. Although a plausible explanation is that the process is dominated by the environment, little serious effort has been devoted either to describing the reservoir itself or to determining the probable effect of the reservoir properties on the process. This study is intended to be exploratory in nature; however, it is hoped that it will provide additional insight into the physical problem and that it will suggest areas suitable for further investigation. EXPERIMENTAL COMPUTATION MODEL To limit the observed dispersion to that which results solely from variations in the properties of the porous medium, an idealized process in which one incompressible fluid displaces another identical fluid is simulated. This simulation is achieved by means of a modified Monte Carlo method — by tracking a number of mathematical particles (tracer) through the system according to the steady-state, single-phase velocity distribution. Then the system is characterized by the distribution of the residence times of the particles. Since any number of particles can be injected simultaneously (a true delta-function distribution) and only pressure conditions are imposed on the boundaries, the model is completely determinate. Furthermore molecular diffusion, microscopic dispersion, adsorption and/or reaction are automatically precluded from the model. The heterogeneous medium is represented by a rectangular, three-dimensional array of uniform, homogeneous porous blocks which are randomly arranged; it is assumed that any two opposing faces of the system are held at fixed potentials

Jan 1, 1965

By J. N. Chew, C. A. Connally

A correlation is presented for predicting the viscosity of gas-saturated crude oils under reservoir conditions. It is based on the dead oil viscosity and the solution GOR. The correlation was developed from a study which showed that at a fixed solution GOR, the relation between the gas-saturated oil viscosities and the correrponding dead oil viscosities is a straight line on logarithmic coordinates. Data from 457 crude oil samples from the major producing areas of the U. S., Canada and South America were used. The best straight lines through the data were fitted by the method of least squares with a digital computer. The correlation is presented in the form of an equation and also in a convenient gra-phical form. INTRODUCTION The viscosity of gas-saturated crude oils under reservoir conditions is an important physical property used in reservoir engineering calculations. Many difficulties are inherent in the sampling of gas-saturated oils and in the laboratory measurement of their viscosities. Therefore, it is frequently neither possible nor convenient to obtain measured values, so the viscosity must be estimated from other, more readily available data. This paper presents a correlation for predicting the viscosity of gas-saturated crude oils. The correlation is based on the amount of gas in solution and the viscosity of the dead oil at the temperature of interest. A previous correlation of these variables was presented by Beal. In comparison, the correlation presented here extends to a higher GOR and to a lower dead oil viscosity. Over the range of variables covered by both, this correlation is based on approximately 11 times as many oil samples. DEVELOPMENT OF CORRELATION A study was made of the variables or parameters which could be used to relate the viscosity of a gas-saturated oil to its dead oil viscosity. Preference was given to those variables which are easily and commonly measured in the field or in the laboratory. It was found that either the differential liquid formation volume factor or the solution GOR of the gas-saturated oil could be used as a correlating parameter. The solution GOR was se- lected for the correlation because of its simplicity and availability. In an attempt to refine the correlation by introducing a second parameter, the following additional variables were tested: differential liquid formation volume factor at the reservoir bubble point, the formation volume factor at the saturation pressure for the GOR of interest, reservoir temperature, viscosity of C+ fraction at 100°F and atmospheric pressure, weighted average gravity of gas in solution, oil gravity, reservoir bubble point pressure, saturation pressure at the selected GOR and reservoir temperature, and gas mol fraction. None of these improved the correlation to any significant extent. It was found that at any fixed solution GOR, the relation between the gas-saturated oil viscosities and the corresponding dead oil viscosities is a straight line on logarithmic coordinates, for the range of variables investigated. This straight-line relationship was used for the correlation. Viscosity data on a total of 457 crude oil samples were used. The data were obtained with rolling ball-type viscometers. The samples came from all of the important producing areas of the U. S., as well as from Canada and South America. Their geographical distribution is shown in Table 1. The ranges of properties represented by these samples are as follows: For each crude oil sample the viscosity of the liquid phase from each step of a differential liberation was plotted against its solution GOR on semi-logarithmic paper. A smooth curve was drawn through the points and values of viscosity in centipoises were read from

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By R. E. Goodman, M. A. Mahtab

The, state of stress around a vertical wellbore in rock following nonlinear stress-strain laws is examined by means of finite element analysis. The wellbore, is considered an axisymmetrier body with axisymmetric loading. The initial vertcal and borizontal stresses are "locked" in the rock elements around the wellbore and a new state of stress is generated by the displacements which occur around the borehole. A point-uise variation of the elastic moduli is made on the basis of the new stress state and the triaxial data. The initial stresses tire now reintroduced along with tile changed moduli and original boundary constraints. This procedure is repeatrd until convergent stresses are reached. The effect of nonlinearity on streases is examined for a 6,000-ft wellbore in a scbistose gnezss and Berea sandstone using results of laborratory triaxial compression tests. The results sbou that the effect is restrited to one well radius from the bottom periphery of the bole. Beyond a distance of one-quarter radius, the elfect of nonlinearity on stresscs IS almost always less than percent for the cases conszdered, The consideration of a static pressure inside the well does not magnify the effect of monlinearity on borehole stresscs. INTRODUCTION The terms " wellbore" and "borehole" here designate cylindrical openings in the ground with vertical axis and a circular cross-section. A knowledge of the stress redistribution that occurs on excavating a wellbore is important in understanding (1) the behavior of the lined or unlined hole, (2) hydraulic fracture response, and (3) the effect of stress redistribution on drillability; also it is important in predicting initial stresses in the virgin ground, and in analyzing the response of measuring instruments placed in the borehole. Our knowledge of the state of stress around a wellbore has been restricted to homogeneous, isotropic, elastic material and derives chiefly from the analysis by Miles and Toppingl and the photoelastic work of Galle and Wilhoit2 and Word and Wilhoit.3 In this investigation the state of stress is examined for a nonlinear elastic material by means of finite element analysis. Many rocks possess stress-strain curves that depart notably from straight lines in their initial or final portions. While the literature contains abundant stress-strain data from triaxial tests (axisymmetric loading) on cylindrical rock specimens, there is little information on rock deformability under nonaxisymmetric loading conditions such as occur at each point around the bottom of a wellbore. Although there is some knowledge of the effect of intermediate principal stress on rock strength, there is virtually nothing known about its effect on rock deformability; therefore, we have assumed here that the effect of intermediate principal stress can be ignored. A schistose gneiss4 and Berea sandstone5 were selected as representative rocks for this analysis. The traditional graphs of deviator stress (ol -o3) vs axial strain were reworked to give the tangent modulus as a function of the deviator stress for varying values of the minor principal stress. The result is a nesting family of skewed, bell-shaped curves for tile gneiss (Fig. 1A) and the sandstone (Fig. 2A). A similar replotting of the lateral strain data defines the variation of Poisson's ratio (v) with the deviator stress and confining pressure. These curves, shown in Fig. 1B for the gneiss and in Fig. 2B for the sandstone, are not so well ordered as the tangent modulus curves. However, all of these display an increase of v with deviator stress application, but the rate of increase diminishes with confinement. The ET and v curves for the two rock types are tabulated in Tables 1A and 1A for use in a digital computer so that material properties corresponding to a given state of stress can be assigned by interpolation. STATEMENT OF THE PROBLEM Given a state of stress in the ground prior to drilling a hole (initial stresses), we assume that

Jan 1, 1969

By R. P. Alger, M. P. Tixier, D. R. Tanguy

In the combination induction-electrical log used at present in the field, the induction logging tool is appropriate for the investigation of moderately invaded formations. A new induction sonde with a radius and investigation about twice as large has been developed recently for the case of deep invasion. It has very nearly the same vertical resolution as the present sonde so that thin beds are defined as accurately as before. The characteristics of the new tool are described, the corresponding interpretation charts are given and field examples are discussed. The design of the sonic logging tool has been modified to improve the calibration and the reliability. The fact that porosity can be accurately recorded by means of the sonic log has prompted new interpretation procedures for saturation estimation, wherein the data concerning the various permeable beds in a given well are correlated. One approach consists of plotting transit time vs true resistivity, with an appropriate scale. With this approach, saturations can be estimated conveniently even in cases where formation water resistivity is not well known. In another approach, a comparison is made of the values of the formation waters computed from the re- sistivity and sonic logs. Using the concept of continuity, this procedure makes possible a quick determination of zones of saturation in shaly sands and/or in case of appreciable variations of formation salinities with depth. It has been found that the comparison of porosity from the sonic log with the apparent porosity computed from a short-investigation resistivity log may reveal, in many cases, the presence of residual oil and thus detect potentially productive formations; this procedure is valuable when the true formation resistivity and the resistivity of the formation water are in doubt. INTRODUCTION During the past year, the efficiency of log interpretation has been vastly improved. The improvements have largely resulted from the introduction of a deep-investigation induction device and from the application of new interpretation techniques that utilize sonic vs resistivity readings. Since the new interpretation techniques depend, in part, upon good values of true formation resistivity, the new induction log will be discussed under Part I. The sonic interpretation techniques will be studied under Part 11. Early in 1959, the 6FF40 induction equipment was introduced in the field. This device was designed for a better approach to true formation resistivities in deeply invaded zones. The greatly improved radial investigation of the 6FF40 equipment has been achieved without sacrificing vertical resolution. The first combination induction-electrical log, the 5FF40, was introduced as a standard tool in 1956 for the logging of wells drilled with fresh muds. The tool has received wide industry acceptance in the United States. 'The 5FF40 induction log has a radial investigation sufficient to overcome average depths of mud filtrate invasion. At 5d invasion, for example, the 5FF40 induction log will read about 1.4 R. in a water sand where R., = 10R,. At 10d invasion, such induction log would read 2.45 R. in the same water sand. In either case, the effects of invasion would not be sufficiently great to cause a water sand to be mistaken for a shale-free oil- or gas-producing zone. Some formations, however, invade deeply — in excess of 10d. Such water zones could be mistaken for oil-or gas-saturated sands unless the porosity balance' can clearly make the distinction. It is for these deeply invaded formations that the 6FF40 was developed. CHARACTERISTICS OF THE 6FF40 Radial Investigation Characteristics To describe the comparative responses of the 5FF40

By W. A. Vine

Next year, in 1964, Butte will celebrate its Centennial. It was in May, 1864, that the first recorded mining activity took place. During that summer, several rich placers were found on Silver Bow Creek and its tributaries, and a gold rush followed. As placer mining proceeded in the creek beds, the quartz lodes on the hillsides were located and the veins were prospected. Mining in Butte entered its second phase when the rich silver mines, the Alice, Moulton, and Lexington, were opened. The silver boom lasted until the decline in the price of silver in the early 1890's forced the closure of many of the mines. An indication of the beginning of the copper mining era in Butte was in 1866 when it was noticed that green copper carbonate discolored some of the, lode material. It was not until ten years later, however, that the Anaconda and St. Lawrence claims were located by Michael and Ed Hickey. The claims were sold in 1880 to Marcus Daly and in 1881, Daly obtained financing and organized the Anaconda Silver Mining Company to exploit the vein The silver venture was a failure because of the predominance of copper which diluted the bullion to only 400 fine.

Jan 1, 1963

By D. M. Wyslouzil

"Micron or sub-micron size gold inclusions in sulphide minerals cannot be extracted by conventional cyanidation. The gold surfaces must first be exposed by decomposition of the sulphides. As an alternative to roasting, pressure oxidation was found to be a most satisfactory method to decompose the sulphides and expose the gold particles. For cyanidation the pressure oxidation pulp has to be neutralized and stabilized with lime. It was found that thiourea can extract the gold directly from the pressure oxidation pulp without pH adjustment and oxidant addition. The main obstacles against the common use of thiourea are circumvented by a recently described control method of the emf during leaching.INTRODUCTION Amalgamation and cyanidation are the most conventional processes for gold extraction. The prerequisite for gold extraction is the possibility of gold surface to be contacted by mercury or by the cyanide solution. Encapsulated gold has little chance of contact and this leads to poor extractions.The reasons why a gold ore may be refractory are: micron or sub-micron size gold particles included in the sulphide minerals, such as pyrite and arsenopyrite; presence of and association with antimony, arsenic, tellurium and carbonaceous minerals. Some alternative processes, such as double oxidation(1,2), pretreatment with lime , H202, chlorine and Caro's acid, roasting and thiourea leach, have solved some of the problems of ""refractory"", but the sub-micron gold in sulphide minerals still shows little response. Roasting and the cyanidation of the calcine was one of the most successful approaches for this type of gold ore.There are two disadvantages to the roasting process: (1) the generation of sulphur, arsenic, antimony and mercury containing gases is undesirable and the control is extremely expensive; (2) gold particles might be fused in the roasted product and the oxidized base metals in the calcine might reduce the cyanidation efficiency. In recent years the pressure oxidation process has been considered as one of the more effective and satisfactory methods to decompose the sulphide minerals and expose the gold surface to the cyanide leach solution. The pollution problem could be better controlled and the gold extraction is more amenable."

Jan 1, 1985

By H. R. Hanley

The characteristics of alloyed anodes and their influence on the products of electrolysis and power consumption have been noted previosly ously in the literature.' This paper presents data in continuation of the subject given in an earlier paper by the authors.2 As noted in the authors1 previous paper, the objectives of this work are the reduction in the cell voltage and the purity of the cathode product resulting from the use of alloyed lead anodes. The fundamental facts developed in the previous paper were: (I) that the presence of a small amount of calcium lowers the anode potential approximately 50 per cent. below that of pure lead; and (2) that thallium when present to the extent of 4 per cent. rendered the anode practically stable, thereby lowering the contamination of the cathode by lead to a very insignificant amount. The specific features determined in this recent work are as follows: 1. The lowest limit of calcium in the lead which will still give maximum lowering of the anode potential. 2. The characteristics of the thallium-calcium-lead anode. 3. The characteristics of the silver-calcium-lead anode. 4. The characteristics of the thallium-silver-calciurn-lead anode. It was determined that 0.1 per cent. calcium in the anode was sufficient to lower the anode potential approximately 50 per cent. Table 1 shows the characteristics of alloyed anodes tested. The anode composed of 0.1 per cent. calcium, 4 per cent. thallium, and 95.9 per cent. * Professor of Metsllurgy, Missouri School of Mines. t Professor of Metallurgy and Ore Dressing, Hea.d of Department, Missouri School of Mines. Assistant Professor of Metallurgy, Missouri School of Mines. 1 Among others, see C. G. Fink and Li Chi Pan: Insoluble .Anodes for the Electrol-ysis of Brine [Trans. Amer. Electrochem. Soc., (1926) 49, 83-1341 and other papers by these authors. U. CJ. Taintori, 8. G. Taylor arid H. P. Ehrlinger: Lead Alloys for Anodes in Electrolytic Production of Zinc of High Purity. Truns. A. I. M. E. (1929) 192-200. 2 H. R. Hanley, C. Y. Clayton, D. F. Walsh: Investigation of Anodes for Production of Electrolytic Zinc. Trans. A. I. M. E. (1930) 275

Jan 1, 1931

By James G. Mock

The choice of equipment to be applied to a given installation by the Application Engineer begins with the data as presented to him by the user. This point in the relationship establishes a communication link, which will decide whether or not the correct piece of Overhead Equipment is applied at the most economic advantage to the user. The role played by the user cannot be minimized. No one knows better than he, just what work he expects to accomplish with this piece of machinery. However, all too often, he oversimplifies the requirements, and along with minimal crane and building parameters, merely refers to one of the following crane classifications as defined by The Crane Manufacturing Association of America, as shown in Figures 1, 2, 3, 4, 5, 6 and 7. This approach places the ultimate user in an unfair position, since he has then assumed the status of the machinery designer and must, therefore, assume the responsibility of the success or failure of the operation of that piece of machinery. If the user selects a Class "C" crane for his job requirement, when actually a Class "B" crane can adequately handle the work load, he is not offering the most economic solution to his company and added little to the cranes service capabilities.

Jan 1, 1973

By G R. Mould

The paper presents a general background to the subsidence research program being undertaken by the Department of Mineral Resources and Development in New South Wales. The results of the studies undertaken over the last ten years are summarised. The differences between these results and those obtained by the National Coal Board are discussed. The results of a study carried out on the effect of total extraction beneath a freeway in the southern coalfields are discussed in some detail. The procedures developed for the construction of a 500 mm diameter natural gas pipeline crossing a number of collieries in the northern coalfields are also outlined. The future direction of the Department's subsidence research program is discussed.

Jan 1, 1980

By J. P. Rider, T. W. Beck, J. A. Organiscak

"The National Institute for Occupational Safety and Health (NIOSH), Pittsburgh Mining Research Division (PMRD) has recently developed a series of models utilizing computational fluid dynamics (CFD) to study gas distribution around a continuous mining machine (CM) with various fan-powered flooded bed scrubber discharge configurations in an exhaust curtain working face. CFD models utilizing species transport model without reactions in FLUENT were constructed to evaluate the redirection of scrubber discharge toward the mining face rather than behind the return curtain. The study illustrates the gas distribution in the slab (second) cut. The following scenarios are considered in this study: 100% of the discharge redirected back towards the face on the off-curtain side of the continuous miner; 100% of the discharge redirected back towards the face, but divided equally to both sides of the machine; and 15% of the discharge redirected toward the face on the off-curtain side of the machine, with 85% directed into the return. These models were compared to a model with a conventional scrubber discharge where air is directed away from the face into the return. The models were validated based on experimental data and accurately predicted sulfur hexafluoride (SF6) gas levels at four gas monitoring locations. One additional prediction model was simulated to consider a different scrubber discharge angle for the 100% redirected, equally divided case. This paper describes the validation of the models based on experimental data and the gas distribution results of the CFD models. INTRODUCTION To control methane gas and dust concentrations on continuous mining operations, it is important to provide sufficient quantity of fresh air from the end of tubing or curtain to the active face. In this region, operating machine-mounted water sprays and fan-powered, flooded bed scrubbers can significantly increase the amount of airflow reaching the face [1-3]. However, when an entry is large, especially in higher coal seams, the water spray configuration and the scrubber capacity may not be adequate to maintain sufficient forward airflow to confine the dust cloud to the face. Dust can roll back toward the machine operator as a result [4]. Currently, several coal mines having negligible gas emissions in higher coal seams (2.4 to 3.0 m [8 to 10ft.] thick) with exhaust tubing systems redirect the scrubber discharge back towards the face in an effort to improve dust collection. NIOSH studied the redirected scrubber exhaust techniques for dust and gas control in a full scale CM gallery to assess its potential for industry-wide application [5]. For a CM face, previous studies have concluded that the behavior of gas and respirable dust is a complex process. The distribution/dispersion and transport of gas and respirable dust after they are liberated at the face are governed mainly by their mass properties, the movement pattern of the ventilation air, and interactions with the mining machine and water droplets created by the external water spray systems used for dust control [6-10]. To understand these behaviors in a complex CM environment and to evaluate the effectiveness of various control techniques, numerical modeling has become a necessary supplement to laboratory experiments and field studies."

Jan 1, 2017

By S. Kivrak

The firms in construction industry could not sufficiently adapt the rapidly emerging information technologies in recent years into their corporate structures. Therefore, in an effort to further exploit the benefits of information technology (IT), integration of the experiences and backgrounds of construction industry and the advantages of IT, is one of the most open-ended fields for improvement in this industry. Utilization of IT in the construction sites will positively affect the efficiency, productivity, quality and health & safety issues in the construction sites thus the cost and completion time of the projects. Within this context, augmented reality technology, which brings a new perspective into IT, can be put into the service of construction industry. Augmented reality which has been designed to improve the services in many application domains such as school education, military warfare, military trainings, industrial maintenance, retail and medical, can be defined in the simplest form as augmenting the real world with information from the virtual world. The main aim of this study, which presents an overview of an ongoing project, is to develop an innovative method by making a construction worker, foreman, equipment operator or a site engineer watch a very comprehensive and informative animation which will enable the said staff to perform or supervise all the phases of the activity he or she is in charge for in a more efficient, productive, safer and qualified manner by means of smart glasses using augmented reality systems. In this respect, training material related with the activities in the construction sites will be prepared and with a well-fictionalized scenario, animations exhibiting all the phases and details regarding the related activity (e.g. masonry, formwork and rebar works etc.), method of statement, correct and incorrect applications in comparison-wise manner, will be produced. Therefore, the user will be able to reach the training material, method statements etc. in the animations about the activity he or she is in charge for, enabling him or her to figure out the work as prescribed in the specifications. Basic trainings about the system will be given to target group, i.e. construction workers, foremen, operators, site engineers and managers working in the construction sites to apply the system on sites after all the system was tested. After the testings, to determine the effectiveness of this system, semi-structured interviews and survey questionnaires will be conducted among the mentioned target group. Therefore, the potential benefits of this system to the construction industry can be determined. The main target of this study is to implement an efficient, thorough construction management by orienting the staff in the construction sites to perform efficient, safe and qualified works by means of smart glasses that use augmented reality. There are relatively few studies about the implementations of augmented reality technology in construction. The outputs to be attained in the end of the study have the potential of improvement of time, cost, quality and safety parameters by ensuring a qualified, safe, efficient and productive construction management via augmented reality technology in the construction industry.

Aug 1, 2013

By Kenneth Eilerts

The development and operation of "combination wells"5/ have created new and unusual problems, many of which can he solved only if information is available concerning the properties of the fluids produced. Data as to the characteristics of the fluids at the relatively high pressures that exist in the reservoirs are especially important, and there is growing economic concern to know what part, if any, of the liquid recovered at the surface was liquid in the reservoir, As an extension of this problem, it is important to know, whether liquid will be formed in the reservoir as a result of isothermal retrograde condensation when the reservoir pressure is reduced. The pressure range of such condensation, if it occurs, is significant in the design of gas-recycling plants for maintaining reservoir pressures. In connection with the operation of such plants, it is particularly important to know how pressure and temperature will affect the yield of the liquid phase and the composition of the gas to be returned to the reservoir. It has not been possible to predict the behavior of these fluids that have high ratios off gas to liquid by comparing them with the behavior of low gas-liquid ratio fluids at identical pressures and temperatures. Such comparison fails because the proportions in which a component will be distributed between the phases of a system at any given temperature and pressure depend increasingly on the composition of the mixture as the critical temperature and. pressure of the system are approached. Because many combination wells are producing from reservoirs that have temperatures near the critical point, experimental date on the properties of the Fluids under reservoir conditions are particularly important at this time, To meet the immediate requirements of the industry for such experimental information, an equilibrium cell has been constructed at the Petroleum Experiment Station of the Bureau of Mines, Bartlesville, Okla. When adequate experimental date have been accumulated, it may be possible to make dependable estimates of the phase relations for high gas-liquid ratio fluids at the pressures anti temperatures characteristic of "combination-well? reservoirs.

Jan 1, 1940

By L. G. Austin

If S (x) is the specific rate of breakage of size x and B (x, y) (see Table 1 for Nomenclature) is the cumulative breakage distribution function, the Herbst Fuerstenau2 assumption is that Inserting this assumption into first-order grinding equations it has been shown" that there are then simple analytical solutions to the grinding equations, as shown in Table 2. In this context "plug flow" is defined as all material passing through the mill in the same length of time, the residence time t. The term "n fully-mixed" means that the mill has a residence time distribution" which can be treated as if the mill were n equal fully mixed sections in series. In addition it has been shown that the assumption of Eq. 1 also leads to simple analytical solutions for closed-circuit, steady-state grinding with an ideal classifier at the mill exit returning oversize to the mill feed. The solutions are also given in Table 2, with µ as the ideal classifier cut size, C the circulation ratio, and Q (x) the size distribution of the circuit product. The specific surface area of these size distributions is where the density-shape factor k. is assumed to be constant with size. In practice, most methods of size analysis or area [ ] measurement have a finite lower limit, so that the integration is really performed from xm, to xm, For a realistic degree of grinding the value of So is dominated by the fine sizes because of the 1/x factor. Consider batch grinding of a feed of size y to y + dy. The batch grinding solution given in Table 2 is then [ ] The fresh surface area produced is the area of the fines plus the area of the original material remaining minus the area of the original material, [ ] Little error is introduced by neglecting the last term on the right-hand side since at t = 0 it is zero, and when t is significant the first term dominates because of the fine sizes produced. In addition, the form of P (x, t) for [ ] realistic values of S (x) 2t ax° is such that the major fraction of fresh surface produced is contained within the bottom 10% of weight of broken material, that is, for sizes for which P(x, t) < 0.1 (providing y is not near x.,). Thus for surface area purposes Eq. 3 can be approximated by [ ] becomes providing again that the feed sizes are coarse relative to xmi. Then the fresh area production is and W is the mass in the mill. The rate of surface production is WK, and the specific surface is Kt. From Table 2, the specific energy is mt/W so surface production per unit energy is [ ] Surface produced per unit energy input = KW/m (8) where m is the energy input of the mill. Clearly, identical reasoning applies to open-cycle, plug-flow grinding, with t replacing t, and Eq. 8 is obtained again. Considering open-cycle, fully mixed grinding, similar reasoning gives P(x) - t S(x) for surface area purposes, and

Jan 1, 1974

By Arnolfo A. Valdivia

Prior to 1971, there were several clinical trials to evaluate programs for early detection of lung cancer. Among these, the Philadelphia Pulmonary Neoplasm Research Project,(3) the Veterans Administration Study published by Lilienfeld,(7) and the controlled trial of the Kaiser Foundation Health Plan showed an overall five year survival rate of 8% for newly detected cases (the same as the national statistic for unscreened patients). In 1971, the National Cancer Institute initiated three randomized, controlled mortality studies using lung cancer screening of persons at high risk (male smokers over 45 years old). The studies are being conducted at the Johns Hopkins University Hospital, the Mayo Clinic, and the Memorial Sloan-Kettering Cancer Center. The studies have slightly different designs in the combination of sputum cytology and chest x-rays. At the Mayo Clinic the study group is offered screening with sputum cytology and chest x-rays every four months, whereas the control group is advised to have an x-ray and cytology every year. No reminders are sent, and it is believed that only about 20% of the control group is screened. At Johns Hopkins and Memorial, both experimental and control groups are offered annual chest x-rays. The experimental group is additionally offered sputum cytology every four months.(5) At present all of the programs show that screening can detect cancers that are undetectible by other means. However, at this time mortality rates in the control and experimental groups are not significantly different in any of the three studies. OUR PROGRAM Our clinic is located in Grants, New Mexico and we provide most of the pre-employment physical examinations for the mines operating in the Grants area (Kerr McGee Nuclear, Homestake Mining, United Nuclear, Western Nuclear, and Ranchers). In the examinations, we obtain the previous mining history of the worker, a chest x-ray, a sample of sputum for cytological examination, and a blood sample. We also provide routine annual physical examinations of the workers, with special interest in the detection of bronchogenic carcinoma. In the early seventies, we did not have a definite surveillance program. We did not know whether we should have a program like the one started at Memorial or like the one started at the Mayo Clinic. After long consideration, we decided to have a program that does not demand a sputum cytology and chest x-ray every four months, but that allows as many chest x-rays and sputum cytologies as needed to diagnose lung cancer as early as possible. We believe that, if a screening method for cancer is to be optimally effective, it must detect the process at stages early enough for curative therapy. We order a test depending on the age of the miner, the race, the mining history, the smoking history, the radiation exposure levels, and the results of the previous chest x-ray and sputum cytology. With the help of the computer, we have a list of all the miners who should be watched closely because of age, race, mining history, smoking history, radiation exposure, etc. Examination of the miners is performed at our clinic, where all the records are kept. The sputum is collected there but examined in Grand Junction, Colorado, by Dr. Geno Saccomanno. There are two ways to collect sputum. The best way is to collect three consecutive morning samples. For this, we need the cooperation of the miners. They have to follow these instructions and mail the bottle containing the sample to Grand Junction. "Instructions for obtaining a good cough specimen" The enclosed plastic bottle contains a preservative solution, so do not empty out the liquid in it. When you go to bed, place the plastic bottle at your bedside where it will be handy in the morning. When you first get up in the morning (before breakfast) try to cough up some "phlegm" from deep in your chest, and spit it into the liquid in the bottle. Try coughing several times. If you have difficulty coughing, try inhaling deeply the steam from a teakettle (or home-type inhalator). Keep the amount of saliva (ordinary spit) that you put into the bottle along with the cough specimen as small as possible. Do not collect the "phlegm" or mucous that comes from the back of your nose. Put the cap back on the bottle, and shake it vigorously for two minutes. If the amount of material you have coughed up is quite small, then keep the bottle at your bedside for three or four days, and each morning try to add another cough specimen. After obtaining your cough specimen, repack the bottle in the mailing container, and attach the enclosed mailing label. It does not require any postage stamps. Unfortunately, some miners "forget" to mail the sample and end up with an incomplete physical examination. To avoid this some companies, like Homestake, request that we obtain the sample in our clinic by forcing cough and expectorant with a nebulizer machine. This method does not give as good a sputum sample as the previous one, but we do get a sputum sample for every miner. The policies of different companies, in regard to annual physical examinations are different. All

Jan 1, 1981

By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By F. M. Doyle, J. P. Dwyer

Introduction The mining industry has a poor public image. It is often perceived as a despoiler of the landscape and a polluter of the environment, and there is little recognition of societal needs for the raw materials and fuels that this industry produces. There are many reasons for this poor image, but an important one is that a substantial number of mining operations have caused significant damage to the environment. Many of these operations, particularly those that now are abandoned, continue to have an adverse impact, principally in the form of water pollution.1 In some cases, the damage caused by this pollution extends well beyond the immediate region around the mine. Chemical contamination of ground and surface waters can, and does, occur in nature when these waters flow through or over undisturbed, mineralized rock masses. However, the problem is greatly exacerbated by mining because the mining activities increase, by several orders of magnitude, the permeability and the surface area of rock that can be contacted by percolating water. Water flowing through either the mine workings or the waste rock dumps becomes contaminated. Pollution can also arise if leachate from tailings ponds enters either groundwater or surface waters. This leachate may contain chemicals used in processing the ore. The magnitude of the threat posed by mining wastes depends on the type of minerals in the deposit, and on the chemicals used to process the ore. The magnitude of the threat also depends on two other, site-specific factors. One is the volume of water flowing into the mine and through the dumps, which depends on rainfall patterns, topography, and whether the mine workings are surface or underground. The other is the proximity of the pollution source to groundwater or surface waters, which depends on both the climate and geology. These factors influence the concentration and the quantity of polluted water forming and reaching the receiving water. Mining activities present a potential problem of enormous scale. Vast amounts of rock are mined each year2 and, as noted above, substantial problems have arisen at some mine sites. These problems are usually exceedingly costly to address, and it is imperative that these mistakes not be repeated. There are indications that we can accomplish this goal; we now better understand the processes that cause pollution and have methods to prevent or contain it. In addition, in the past few decades society has started to recognize the need for all industries to operate in a manner that maximizes the health and safety of workers and the public and minimizes adverse environmental impacts. A variety of recently enacted federal and state laws regulating public health and environmental hazards reflect the increasing concern over these issues. Many statutes, such as the federal Clean Air Act and the Clean Water Act, encompass activities undertaken by the mining industry. Other laws, such as the Surface Mining Control and Reclamation Act, have been written to regulate specific hazards posed by this industry. At the present time, the federal government. through the Environmental Protection Agency (EPA), and several state governments, are preparing new regulations specifically tailored to control the disposal of mining wastes. Given the magnitude of the potential environmental and health risks posed by disposal of mining wastes and the regulatory costs to the mining industry (both of which are due to the tremendous volume of waste generated), it is especially important that regulators have a good understanding of the different types of mining wastes and the risks they are likely to pose in various geographic and climatic circumstances. Only then can a regulatory program be designed with suitable procedures and substantive criteria to protect the environment and ensure compliance, while avoiding unnecessary or wasteful expenditures. California has long enjoyed a large, active mining industry. Today it produces a wide range of mineral commodities. The revenue from production of non-fuel minerals in California ($2.85 billion in 1988) greatly exceeds that of any other state. About a third of this revenue is from the production of inert sand, gravel and crushed stone. However, the remainder is from the production of a wide range of materials. These include boron minerals, rare earths, asbestos, talc and pyrophyllite, and gold. In earlier decades, an even broader range of minerals was produced, including mercury, copper, lead, zinc, and barite. There are acute environmental problems at some of these early mine sites. Because in 1987 the state of California was engaged in a revision of its regulations for mining waste disposal, the legislature commissioned a study by researchers at the University of California at Berkeley to investigate and review: the magnitude of the problem posed by these wastes, • the best feasible control measures available for waste management and disposal, • the problems of abatement and cleanup at so-called "problem" mine sites, • the current regulations imposed on mining waste disposal by various federal, state, and local agencies and the effectiveness of these regulations. This paper summarizes the principal findings from this study (Mining Waste Study, 1988). The lessons from this investigation are likely to be of general interest because of the diversity of mineral products produced, and the wide range of geographic and climatic conditions encountered. The acute problems seen at some of the older mines are typical of the western United States, and teach useful lessons on strategies that should be implemented at new mines to prevent recurrences of these problems.

Jan 1, 1992

By P. L. Hendricks, J. W. Spretnak

The interstitial atom principally responsible for the yield point and strain aging in electron-beam-melted tantalum is identified by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Two sets of specimens contained two levels of oxygen with very low hydrogen contents and the third set had comparable oxygen and hydrogen contents. The activation energy for the return of the yield point agrees well with that for diffusion of oxygen for the first two sets of specimens. For the third set of specimens, the activation-energy value lies between those for diffusion of hydrogen and for diffusion of oxygen. The advent of the dislocation model of plastic deformation in metals has revitalized interest in the yield point and strain aging in bcc metals containing a certain minimum content of interstitial solute elements. Much theoretical and experimental work has been performed in recent years to elucidate the detailed mechanism of these phenomena. The purpose of this investigation is to attempt to identify the principal interstitial element responsible for the yield-point phenomenon in electron-beam-melted tantalum by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Some of the earlier theories of the yield-point phenomenon proposed a grain boundary film of iron carbide. Such models could not satisfactorily explain all features of strain aging and the yield-point phenomena. The most widely accepted explanation is that of Cottrell,1 later extended by Cottrell and Bilby.2 Strain aging is ascribed to "locking" of dislocations by interstitial solute "atmospheres". The yield-point phenomenon results when the dislocations are torn away from their atmospheres. The strain-aged condition is re-established after sufficient time to allow the interstitial atoms to diffuse to the dislocation lines and re-establish the locking atmospheres. Clearly, the Cottrell-Bilby model is concerned with the bulk of the grain and does not specifically involve the grain boundary. The recent modification of the Cottrell-Bilby model is a redirection of attention to the role of the grain boundary and the possibility of multiplication of a limited number of free dislocations rather than unlocking all of the dislocations. Theories have been advanced by Hahn3 and conrad4 which are modifications of the Cottrell-Bilby theory. The model proposed by Hahn indicates that, although the possibility of un- locking anchored dislocations is not excluded, it implies that unlocking is not necessarily required to explain yield drop. Locking of dislocations during the aging treatment is a necessary part of the theory; however, it assumes that dislocations once locked remain locked. It is suggested that the yield drop observed is a result of the following factors: 1) the presence of a small number of mobile dislocations initially, 2) rapid dislocation multiplication, 3) the stress dependence of dislocation velocity. In the case of bcc metals, locking is considered to be the means by which dislocations are immobilized. Cold working of the metal results in the generation of larger numbers of new dislocations and the stress dependence of the dislocation velocity accounts for yield drop observed. Conrad&apos; has proposed a model similar to the one just described which applies to strain aging of iron and steel and which logically could be extended to other bcc metals. This model also does not require large-scale unlocking of dislocations. It is proposed that, during initial loading of a specimen below the upper yield stress, a few dislocations are torn free of their Cottrell atmospheres at regions of stress concentrations. With an increasing stress, some multiplication of dislocations occurs by a double cross slip mechanism, thus giving a preyield microstrain. At some critical stress represented by the upper yield stress, sudden profuse multiplication of dislocations occurs, enabling plastic flow to proceed at a lower stress. In this model, microstrain, preyielding, and flow represent the movement of free dislocations. It should be noted that this model also requires the locking of dislocations by interstitial solute atoms for the occurrence of a yield point; however, unlocking of large numbers of dislocations is not required. If it is assumed that the yield point will return when some fraction of free dislocations produced during pre-straining are pinned, the number of solute atoms required to pin unit length of a dislocation line can be calculated when prestrain and reloading are done at the same temperature and strain rate. Since the migration of solute atoms back to the stress fields of dislocation lines is controlled by the diffusion rate of interstitial solute atoms, it is to be expected that the activation energy for strain aging would be identical to the activation energy for diffusion. It would also be expected that the strain aging observed will be controlled by the fastest diffusing species capable of producing locking over the temperature range investigated. The rate of yield-point return has been found to be adequately expressed by an empirical rate equation of the form: rate=Ae-Q/RT [1] where A = constant, Q = activation energy, R = gas constant, and T = absolute temperature. Cottrell and Bilby2 have expressed the number of atoms per unit length of dislocation line which arrive

Jan 1, 1967

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best&apos;s as deterrirzed by electron-pro be chalq&apos;sis, the slriations roerre fbund to ILUL&apos; no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,&apos; it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations&apos;&apos;, to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.&apos; Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1&apos; or without&apos;3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3&apos;11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium&apos;9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.&apos; High-purity bismuth and antimony, both a 6-nine grade by the manufacturer&apos;s emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967