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By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By T. Y. Yan

SUMMARY Laboratory high pressure column tests have shown that the presence of 1-20 ppm of aluminum ion effectively prevents permeability loss during uranium leaching with leachates containing sodium carbonate. If added after permeability loss has occurred, aluminum ion can restore the permeability to nearly its original value. No deleterious effect was observed on uranium leaching performance and the technique should be quite compatible with all field operations. INTRODUCTION The recovery of uranium values from underground deposits by in situ leaching or solution mining has become economically viable and competitive with conventional open pit or underground mining/milling systems (Merrit, 1971). In situ leaching processes are particularly suitable for small, low-grade deposits located in deep formations and dispersed in many thin layers. Many such ore bodies occur along a broad band of the Gulf Coastal Plain (Eargle et. al., 1971). The advantages of the in situ leaching processes have been reviewed (Anderson and Ritchi, 1968). In the in situ leaching process, a lixiviant containing the leaching chemicals is injected into the subterranean deposit and solubilizes uranium as it traverses the ore body. The pregnant lixiviant or leachate is produced from the production well and is then treated to recover the uranium. The resulting barren solution is made up with the leaching chemical to form lixiviant for re-injection. Upon completion of the leaching operation, the formation is contaminated with leaching chemicals and other species made soluble in the leaching operation and has to be treated to reduce the concentration of these contaminants in the ground water to levels acceptable to the regulatory agencies (Witlington and Taylor, 1978). Restoration is accomplished by injecting a restoration fluid, which could be the fresh water or water containing chemicals, into the formation. As it traverses the leached formation, the restoration fluid picks up the contaminants and is then produced at the production well. This produced water is either disposed or purified for recycle. In both phases of operation, formation permeability or well injectivity is one of the most important parameters which determines the viability of the in situ leaching process. Low formation permeability limits production rates, leading to uneconomical operations. The formation is said to be sensitive if there is a sharp loss of permeability on contact with water and other fluids. Many uranium bearing formations, for example, the Catahoula formation of the Texas Coastal Plain, contain significant amounts of clay minerals which are water sensitive. Serious permeability losses can occur when the pH and chemical composition of the lixiviant is significantly different from that of the formation water. Jones has investigated the influence of chemical composition of water on clay blocking of permeability (Jones, 1964) and Mungan studied permeability reduction through changes in pH and salinity of the water (Mungan, 1965). Various mechanisms of permeability damage have been proposed and reviewed (Jones, 1964; Mungan, 1965; Gray and Rex, 1966; and Veley, 1969). When large amounts of swelling clays are present, a significant fraction of the flow channels in the formation can be reduced due to swelling. However, in most cases, swelling need not be the main cause of permeability losses. Particle dispersion and migration or clay sliming can be more important causes for formation damage. Clay particles entrained in the moving fluids are carried downstream until they lodge in pore constrictions. As a result, microscopic filter cakes are formed by these obstructions, plugging the pores, effectively restricting fluid flow and reducing the formation permeability. Moore found that as little as 1-4 percent clays present in a fine grained sandstone could completely plug the formation if they are contacted by incompatible injected fluids (Moore, 1960). It has been found that injection of NaHC03/Na2CO3 lixiviant into formations with significant clay content often leads to loss of formation permeability and well injectivity. To alleviate this problem a change of the lixiviant composition to KHC03/K2CO3 has been proposed. At present, however, many in situ leaching operations employ NH4HC03/(NH4)2C03 mixtures as a source of carbonates. This approach has been successfully used in South Texas by Mobil, Intercontinental Energy, Wyoming Minerals and U.S. Steel, etc. The use of ammonium carbonates solutions, however, contaminates the formation and requires a time-consuming restoration operation. The other approach to reduce the permeability loss is to pretreat the sensitive formation with chemicals which prevent clay dispersion and migration. Such chemicals include hydroxy-aluminum (Reed, 1972 and Coppel et. al., 1973), hydrolyzable zirconium salts (Peters and Stout, 1977), hydrolyzable metal ions in general (Veley, 1969) and polyelectrolyte polymers (Anonymous). Still another approach, is to minimize the "shock" caused by sudden injection by gradually changing the chemical composition of the injected fluids from that of the formation water. THE APPROACH Since permeability loss can be an important factor limiting the efficiency and economic viability of the in situ leaching process, a study was initiated on

Jan 1, 1982

By Christopher M. St. John, Michael P. Hardy

INTRODUCTION Geotechnical models, particularly those based on the finite element method, have been available to aid in en¬gineering design of underground mining excavations for over ten years. Despite this fact there are remarkably few cases of their use in mine design documented in the literature. It is therefore to be anticipated that many potential users of these models are relatively unaware of their capabilities and limitations and also of the form and detail of geotechnical data needed for their success¬ful application. This subsection attempts to address this problem by discussing the different types of numerical models now available and by noting how some of them have been used to study a variety of problems associated with underground mining. The subsection concludes by discussing the applica¬tion of the displacement discontinuity method to the de¬sign of possible mining systems for the copper-nickel deposits of northeastern Minnesota. The object of the analyses, which were nonsite specific, was to determine the significance of geotechnical parameters, such as ini¬tial stress and rock structure, on the stability of under¬ground excavations and hence to provide guidance for future geotechnical investigation. NUMERICAL MODELS In the geomechanical design of underground mining openings, use is made of numerical models that repre¬sent or simulate the large-scale mechanical behavior of rock. There has been less interest in analysis involving fluid flow and heat transfer, but with increasing interest in such areas as in-situ retorting and solution mining it is likely that there will be a growing need for numerical models embracing and coupling all three physical proc¬esses. However, the emphasis in this subsection will be on mechanical behavior. Models which simulate such behavior will be divided into two groups: continuum models and discontinuum models. These will be dis¬cussed in turn in order that some insight into alternative solution strategies and their merits may be gained. Continuum Models Almost all geomechanical numerical models must be classed as continuum models even though particular computer codes incorporate special provisions for rep¬resenting discontinuities such as faults, bedding planes, or joints. They are continuum models because they pro¬vide solutions for cases where material behavior is governed by the differential equations of continuum mechanics. Two basic solution strategies for such equa¬tions may be identified immediately: the differential ap¬proach and the integral approach. In the differential approach a means of approximating the differential equations over the entire region of interest is sought. In the integral approach use is made of fundamental solutions from continuum mechanics, and these are used to construct a solution to the whole problem, making approximations only on the boundaries of the region of interest. The several differential and integral methods are identified in Table 1. Differential Methods: Problems in continuum me¬chanics involve the solution of three types of partial differential equations. Two of these govern the behavior in so-called initial value problems, in which variables change both in time and in space. Examples of such problems include nonsteady heat transfer and fluid flow, and stress wave propagation. The last type of partial differential equation governs the behavior in boundary value problems. In these, variation is in space but not in time. Solution of initial value problems may be achieved in two significantly different methods: implicit and ex¬plicit. The differences between these two methods will be illustrated by considering a very simple initial value problem, that of one-dimensional heat diffusion. The equation governing this process may be written as: [ ] where T is temperature, K is thermal conductivity, p is density, c is specific heat, t is time, and x is the spacial coordinate. In finite difference form this equation might be written as: [ ] where the superscripts refer to the time and the sub¬scripts to the spacial location. Several solution strategies for this equation have been used. Two important ones may be illustrated very simply by discussing the signifi¬cance of the superscript * on the right-hand side of the equation. If i + 1 is substituted for * then the second derivative of the temperature with respect to distance is evaluated at the end of the next time step (using tem¬peratures not already known). Such an approach leads to a set of equations involving unknown temperatures and a solution procedure which is referred to as being implicit. The important characteristic of the implicit procedure is that it leads to a set of equations that must be solved for each time at which the temperature dis¬tribution is required. If instead of substituting (i + 1) for the superscript *, i is substituted, the following equation is obtained: [ ] {In this case the new temperature is defined in terms of an already known temperature distribution. The solution procedure is now known as explicit and has the impor¬tant characteristic that there are no equations that have to be stored or solved. A practical advantage of this

Jan 1, 1982

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,' and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6's viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG'S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.' Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By Donna L. Anderson

This U.S. Bureau of Mines report describes a system to determine the position and heading of a continuous mining machine during the maneuvers required at the face area of a mine. The system consists of commercially available angular position sensors and a computer interface developed and tested at the Bureau. The sensors employed are laser-based scanning devices that report the angular location of retroreflective targets within their 90° field-of-view. The targets are mounted on the continuous mining machine; the laser scanners are mounted on an external reference structure. The computer interface consists of a single-board computer-controller programmed to gather and process the angular position information, and to calculate the machine's position and heading relative to the reference structure. A sensor fusion algorithm will be incorporated into the computer interface programming to increase the accuracy and reliability of the system.

Jan 1, 1989

By Clayton M. Rumsey

No producing or developing mines nor known mineral resources are in the Lower Saline Valley Wilderness Study Area. The inactive Bonanza Prospect has low potential for copper-gold-silver resources. Stone and sand and gravel deposits in the WSA do not constitute mineral resources because transportation costs to major markets are prohibitive. INTRODUCTION The Lower Saline Valley Wilderness Study Area (WSA) covers 2,241 acres in southeast California adjacent to and west of Death Valley National Monument (fig. 1). Access to the WSA is by the Saline Valley gravel road 28 mi northerly from its junction with State Highway 190. The junction is about 35 mi southeast of Lone Pine, CA. The WSA is characterized by moderate to steep, sparsely-vegetated slopes; elevation ranges from about 1,800 ft to 3,560 ft.

Jan 1, 1984

The Annual General Meeting of the South African Institute of Mining and Metallurgy was held in Kelvin House, Johannesburg, on Wednesday, 27th August, 1975. Professor R. P. Plewman (President) was in the Chair. There were present 45 Fellows, 37 Members, 8 Graduates, 3 Associates, 4 Students, and 45 Visitors, making a total of 142. The President declared the Meeting open at 16h00. OBITUARIES The President: Ladies and gentlemen, it is my sad duty to announce the death of the following members of the Institute : M. Barcza, an Honorary Life Fellow and Past President of the Institute; J. A. Boyd, F. E. Keep, and J. H. Taylor, Life Fellows ; I. D. B. Corner, C. O'G. Deane, R. E. Gilmour, A. C. Hofmeyr, M. W. Howell, T. J. Robin, and F. S. Steinhobel, Fellows; J. J. Frankel, Member; and T. J. Higgs, Associate. As a mark of respect to the memory of the deceased and in sympathy with the bereaved, I ask you to rise and observe a few moments' silence. MINUTES The President: May we confirm the minutes of the General Meeting held on March 12th 1975 and published in the June issue of the Journal? Agreed. WELCOME The President: It is now my very great pleasure to welcome the many members of our Institute and all the distinguished guests who have honoured us with their presence this afternoon. In particular, I would like to welcome our Honorary President, Mr R. S. Lawrence, President of the Chamber of Mines, and also our Honorary Vice-President, Mr T. L. Gibbs, the Government Mining Engineer. Ons is ook besonder vereer dat dr. Naude, die Wetenskaplike Raad-gewer aan die Eerste Minister, en mnr. C. A. J. Borman, Direkteur van die Witwatersrandse Kollege vir Gevorderde Tegniese Onderwys, hier aanwesig is om die vergadering by to woon. We are also honoured by the presence of some 19 Presidents, Vice-Presidents, and Chairmen of our sister scientific and technical organizations. I would particularly like to welcome Mr Gericke of the South African Council for Professional Engineers, Professor Pretorius of the A.S. & T.S., and Dr Lloyd of F.S.P.E. And then, also the Presidents of the Institute of Welding, Professor Robinson; of the Electrical Engineers, Dr Troost ; of the Certificated Mechanical and Electrical Engineers, Mr Gibbs; of the Geological Society, Professor Maske; of the Land Surveyors of the Transvaal, Mr Course ; of the Assayers and Analysts, Mr Williams; of the Mine Ventilation Society, Mr Martinson; of the Chemical Institute, Mr Goodman; of the Association of Mine Managers, Mr Pretorius ; of the Institute of Foundrymen, Mr Attenborough; of the Production Engineers, Mr Duggan ; and of S.A.F.U.E.S., Mr Avalle. Then, the Chairman of the Council of the Institute of Metallurgists, Mr Snow; the Vice-President of the Town and Regional Planning, Mr Reinecke; the Vice-President of the Association of Consulting Engineers, Mr O'Kell; and Mr Cronje, who is representing E.A.S.A. Finally, the Chairman of the Southern Transvaal Section of the Chemical Institute, Mr Bloom ; the Chairman of the Witbank-Middelburg Branch of our own Institute, Mr Hosking; and the Secretary-Treasurer of our O.F.S. Branch, Mr Bird. We also have with us Mr Trueman; the Deputy Manager of Kelvin House, Mr Mrost ; our Honorary Editor, Dr Glen; Mr Walford; and also some representatives of the Press. Finally, it gives me great pleasure to welcome those who will receive Honorary Life Fellowships tonight, and also the winners of our student prizes. MEMBERSHIP The President: Ladies and gentlemen, I have pleasure in announcing the names of the following candidates, which have been published in accordance with By-Law 5.2.5., and Council has elected them to membership in the following grades: Fellows: R. G. Boswell, R. W. Chadwick, D. R. Hardman, J. A. Holmes, T. J. B. Jones, and R. P. King. Members : M. A. Bridgeford, C. F. Bonney, H. E. Bartlett, L. G. Floyd, A. K. Haines, D. Hatfield, C. G. Heymann, M. J. Howes, J. B. See, E. van Greunen, and S. P. Swanepoel. Associate Members : J. Coetsee and R. P. G. Steyn. Graduates: J. J. de Villiers and J. C. King. Associates: B. J. Bucher, P. A. Combrinck, W. J. N. Gelderblom, L. S. Halasz, J. van Wyk, C. P. Visser, and A. Veress. Students: D. J. Claasens, P. C. Crous, D. H. Murchison, P. A. Rossouw, and J. P. L. Schultz. Company Affiliates: Airco Engineering (Proprietary) Limited and Deelkraal Gold Mining Company Limited. There have also been some transfers: Member to Fellow: J. B. Nangle. Graduate to Member: E. E. Eichenbergen, M. J. Hillbeck, L. A. Melis, P. J. Venter, and R. O. Wellman. Associate to Associate Member: B. M. Williams. I welcome the newly elected members to the Institute, and I congratulate those who have been transferred to a higher grade.

Jan 10, 1975

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony' states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By J. Sottile, J. L. Kohler

Component failures in the electrical control circuits of mining machines account for a large percentage of the total downtime of the machine. Once a failure has occurred it is always a tedious and usually a time-consuming task to locate the failed component. Moreover, the pressure to quickly locate the cause of a delay can lead to compromises in safety. Thus an onboard diagnostic system, essential for an automated machine, would be a very useful addition to existing machines. This report details U.S. Bureau of Mines development of a generic procedure for synthesizing diagnostic systems for electrical-control-circuit failures in mining machinery. A continuous mining machine is used as the testbed to illustrate the application of the developed methodology. Substantive differences among mining machine control circuits made it impossible to achieve a generic diagnostic system, but a generic approach for the synthesis of the diagnostic system was possible. As the research progressed, it became apparent that an algorithmic approach was better than an expert- system-based implementation. A prototype system was constructed and used to evaluate the diagnostic system. Prototype implementation issues are also examined.

Jan 1, 1993

By Jan Tegtmeier, Horst Gerhardt

INTRODUCTION Under certain circumstances the closure of former mines which are located above a certain flood level can result in problems such as the emanation of detrimental substances after having completed filling and reclamation operations. This especially applies to uranium mines in which the radiation dose could far exceed the dose of natural background radiation. By means of an example of the uranium mining in Germany in the following it will be demonstrated how to cope with this problem. On the basis of comparative investigations in various vein deposits and using ventilation scheme calculations proposals for the optimization of the necessary forced ventilation can be submitted. REPORT ON SITUATION In the period 1946 - 1989 the former Soviet-German joint- stock company "Wismut" developed into the biggest European uranium producer with a total output of about 220.000 t of uranium. A major mineraldeposit district was the deposit of Schlemaf Alberoda in the Saxon Ore Mountains, in which 80.000 t of uranium were produced. Thus it is among the biggest uranium de- posits of the world, from which various other metals were at- tracted for many centuries. The exploitation of the Schlemal Alberoda deposit involved steep veins in regions near the surface as well as depths of 1.800 m. Until 1991 a total excavation space of 40 million m3, which is flooded at present, was produced. With the average increase in the water level of 80 cm per week the final flood level is expected to be reached in the year 2003. The shaft 373 at present still being used for ventilation will be no longer available since the second quarter of 1998 after flooding the -540 m level because it is not connected with the excavation system near the surface. As a study shows, a radiation dose far above the natural back- ground radiation has to be expected for the town of Schlema due to the extensive mining activities near the surface and due to the subsequent displacement with missing depression fo the main mine ventilating fan. An uncontrolled air flow containing radon leaves the open mine excavation due to the effect of the natural ventilating pressure and emanation caused by the barometric pressure drop with atmospheric pressure fluctuations. This mine air with its high-level radioactive equilibrium results in a high radiation dose in buildings (see Figure l). After having switched off the main ventilating fan in order to investigate the effect of the missing depression the increase in radon concentrations amounted up to 700% in various buildings of Schlema. This was partially due to the inversion state of the weather at that time. The high radon concentration has detrimental effects on the health of the population and of the miners working on the further reclamation in regions above the flood level. ANALYSIS OF THE RADON EMANATION RATE EXPECTED Considering the composition of the radon inflow from the mine workings it becomes evident that 80 % of the radon inflow originates from abandoned excavations and only 20 %from open ventilated mine excavations. This fact has to be taken into account for the ventilation after having reached the final state of flooding. After completing ventilation the radiation dose on the surface is mainly due to the radon emanation from excavations close to the surface. Investigations of the Wismut GmbH showed the in- crease in the specific radon emanation rate by a factor of 100 for abandoned excavations as compared to new drivings. One reason is the larger specific surface of abandoned galleries caused by displacements due to mining activities as well as by fall of hanging. Furthermore the radon can enter the gallery through joints, which have subsequently opened by convergences. All these effects result in a larger free surface available for radon diffusion. The large number of drivings in the deposit sections near the surface and the fact that the highest uranium contents are found near the surface as well as the high fracturing are further reasons for higher emanation rates. Considering these facts it can be expected that the radon inflow of 10.000 kBq/s, which refers to an open mine excavation of about 1.4 million m3, represents a minimum. Only by increasing the specific surface, for which a numerical value has still to be determined, this value will increase with certainty. An extensive radon emanation from the residual excavation, which cannot be flooded, can only be prevented by maintaining the ventilation system. The low pressure produced by the fan in the mine openings prevents the emanation of air containing radon due to the effect of the natural ventilating pressure. Without the controlled withdrawal of the radon the population as well as the miners working on the further reclamation in areas above the flood level would be endangered. Therefore the follow-

Jan 1, 1996

By R. E. Powers, E. H. Kinelski, H. A. Morrissey

A group of 17 American blast-furnace sinters, an American open-hearth sinter, an American iron ore, and a Swedish sinter were used to evaluate testing methods adapted to appraise sinter properties. Statistical calculations were performed on the data to determine correlation coefficients for several sets of sinter properties. Properties of strength and dusting were related to total porosity, slag ratio, and total slag. Reducibility was related to the degree of oxidation of the sinters. THIS report to the American iron and steel industry marks the completion of a 1949 survey of blast-furnace sinter practice sponsored by the Subcommittee on Agglomeration of Fines of the American Iron & Steel Institute. The use of sinter in blast furnaces, sinter properties, raw materials, and sinter plant operation have been reported recently.1,2 After preliminary research and study," test procedures were adapted to appraise the physical and chemical properties of sinter to determine what constitutes a good sinter. During the 1949 to 1950 plant survey each plant submitted a 400-lb grab sample to research personnel at Mellon Institute, Pittsburgh, Pa. A 400-lb sample was also submitted from Sweden. In addition, 2 tons of group 3 fines iron ore were obtained from a Pittsburgh steel plant. The following tests were performed on the iron ore sample and on the 19 sinter samples: chemical analysis; impact test for strength and dusting; reducibility test; surface area measurements, B.E.T. nitrogen adsorption method; S.K. porosity test; Davis tube magnetic analysis; X-ray diffraction analysis for magnetite and hematite; and microstructure. Results of these evaluations are discussed in this paper and supply a critical look at testing procedures used to determine sinter quality. Sinter Tests and Results Each 400-lb grab sample of sinter was secured at a time when it was believed to represent normal production practice at each plant. It was not possible to use the same sampling procedures throughout the survey; consequently samples were taken from blast-furnace bins, cooling tables, and railroad cars. These were very useful for evaluation of test methods, since they were obtained from plants with widely divergent operations. With the exception of Swedish sinter and sinter sample N, which were produced on the Greenawalt type of pans, all survey sinters were produced on the Dwight-Lloyd type of sintering machines. Sinters submitted for test were prepared in identical manner by crushing in a roll crusher (set at 1 in.), mixing, and quartering. To secure specific size fractions for tests, one quarter of the sample was crushed in a jaw crusher and hammer mill to obtain a —10 mesh size. The remainder was screened to obtain specific size fractions. The group 3 fines iron ore was dried and screened and samples were taken from selected screen sizes to be used for various tests. Prior to testing, each ore sample except the —100 mesh fraction was washed with water to remove all fine material and was then dried. This iron ore, a hematitic ore from the Lake Superior region, was used as a base line for comparing results of tests on sinters. The iron ore did not lend itself to impact testing, since it was compacted rather than crushed in the test, and no impact tests are reported. However, the iron ore was subjected to all remaining physical tests to be described. Chemical Analysis: Table I presents chemical analyses performed on the survey sinter samples. Included in this table are data obtained from determination of FeO and the slag relationships: CaO + MgO and total slag (CaO + MgO + SiO, SiO2 + Al2o3 + TiO2). The percentage of FeO was used as an indication of the percentage of magnetite in the sinter. It was believed that slag relationships could be correlated with sinter properties. During initial determination of FeO great disagreement arose among various laboratories, both as to the results and the methods of determining values. Table I lists the values of FeO resulting from the U. S. Steel Corp. method of chemical analysis,' which reports the total FeO soluble in hydrochloric and hydrofluoric acids (metallic iron not removed) with dry ice used to produce the protective atmosphere during digestion. Use of dry ice was a modification required to obtain reproducible results. In this method, the iron silicates and metallic iron are believed to go into solution and are therefore reported as FeO. This is important, for in the study of the microstructure of sinters, glassy constituents suspected of containing FeO as well as crystallized phases of undetermined identity which may also contain FeO have been observed. Strength Test by Impact: In evaluating sinter quality, one of the properties stressed most by blastfurnace operators is strength. This strength may be described as the resistance to breakage during handling of sinter between the sinter plant and the blast-furnace bins. It is also the strength necessary to withstand the burden in the blast-furnace. After

Jan 1, 1955

By H. Lyn Bourne

This is the sixth annual tabulation that gives mineral royalty information. This tabulation, like the previous editions, includes all of the earlier data plus more than 100 new entries. In addition to the royalty information, some entries show the cost of purchased reserves. An article in the December 1984 Kentucky Coal Journal could have far reaching applications. It explains that a banking firm examined the "reserve risk" as one of six factors for analysis when financing a coal project. The firm concluded that coal reserves in Kentucky are worth an average of $0.29/t ($0.26 per st) in-place. The banking firm based this in-place value on its examination of more than 50 leases. In-place value is especially important when trying to establish a mineral value for a given deposit. Ernie Lehman wrote to this author after last year's column appeared and he quoted the lease rates for lead and zinc on federal land. He states, from first hand information, that the leases are based on a percentage of net smelter return as follows: 4% for the first five years, 4.5% for the next five years, and 5% thereafter. The figures used in last year's column ($ per st) came from dividing reported royalty income by reported production. The information reported last year merely translates the results of the net smelter return (as written in the lease) to royalty income per ton to the US Government for the various years. Statistics from the Minerals Management Service of the Federal Government show that oil and gas account for 40% and 53%, respectively, of the Federal royalty income. Coal accounts for about 4% and all other minerals, the remaining 3%. Oil and gas leases are mostly at 12.5%. Most of the coal leases are at 12.5% for surface mining operations and 8% for underground mining. Many of the other commodities are leased at 5%, which has been true for decades. Relative to Federal leases, this year's table shows some percentages and some costs per ton. This was done to give information about the leases and also to show income produced by various commodities. Note that some commodities have a variation in $/ton even though the royalty percent is the same. These variations result from a combination of factors that influence the value of a mineral commodity. The same caveats that have appeared in previous columns relative to factors that influence the value of reserves are restated. The data in the table serve as a general reference and are not intended to present an absolute scale of reserves costs. Several factors influence the value of any mineral commodity. The factors include: • location/transportation (especially significant for most industrial minerals); • market conditions both for the commodity and the company acquiring the right to mine it; *quality or grade of the deposit as it reflects the amount of processing/beneficiation necessary to produce the finished product; and • legislative restrictions and conditions for mining a given material at a given site. These and other factors will significantly influence the cost of reserves. The table shows the range of royalties and the variations in the basis of computing the fees. In a few instances, it gives the cost of acquired reserves based on purchase price and quantitative estimates of the material in place. The table lists the commodity in column 1, and the subsequent columns give the location - either by state, US geographic area or Canadian province; the cost - R for royalty and P for purchased cost; and the year in which the lease or purchase agreement occurred. The last column offers either comments or gives a footnote number for more information. The cost column requires more explanation. The units may refer to cubic yards (/yd), cubic feet (/cu ft), tons (/T, 2000 lbs) or acres (/A). 1 cu yd = 0.7646 m3 1 cu ft = 0.2832 m3 1st=0.9078t 1 acre = 0.4047 hm or m2 In several cases, the royalty is a percentage of the sales price of the finished product and is levied against either the amount produced or the amount sold. We thank those who contributed information for the table: G. Anderson, B. Brown, R. Ganis, K. Hauser, E. Lehman, and S. Sims. Their help is appreciated as are the contributions by those who asked to remain anonymous. This column requires additional information each year. That data must come from people in the minerals industry who have royalty information. What appears in the table is only a very small fraction of the cost information relative to the various commodities and the geographic areas for which there is royalty information. If you find this column of interest and possess information write the author at the address given in the author's box or call 313-462-0005.

Jan 7, 1988

The Annual General Meeting of the Institute was held in Kelvin House, Johannesburg, on Wednesday, 22nd August, 1973. Dr J. P. Hugo (President) was in the Chair. There were also present 64 Fellows, 20 Members, 5 Associates, 3 Students, and 34 Visitors, making a total of 126. The President declared the meeting open at 4.05 p.m. OBITUARIES The President: It is my sad duty to announce the death of the following members of the Institute C. Boocock, R. J. G. Moore, M. P. Pearse, and A. I. Sussman, all Fellows, and W. T. Dalling, a Life Member. As a mark of respect to the memory of the deceased and in sympathy with the bereaved, I ask you to rise and observe a few moments' silence. MINUTES Die President: Item twee op die agenda is die bekragtiging van die notules van die jongste Algemene Vergadering van die Instituut. Daar die notules in die Augustus uitgawe van die Joernaal gepubliseer is, vra ek u toestemming dat dit as sulks bekragtig word. Toestemming verleen. WELCOME TO VISITORS The President: It is my very great pleasure to welcome all the distinguished guests who have honoured us with their presence this afternoon; in particular, a hearty word of welcome to the Honorary President of the Institute, Mr Plumbridge, the President of the Chamber of Mines. You are doubly welcome here, sir, and we thank you for your presence. Also to that old member and stalwart, the Honorary Vice-President of the Institute, Mr Tommy Gibbs, the Government Mining Engineer-you're very welcome, Mr Gibbs. Then, we are particularly privileged this afternoon to have an Honorary Member with us, the Minister of Mines for Rhodesia, Mr Dillon. You will recall that he honoured us with his company last year. Mr Dillon, we are very appreciative and hope that this is now a standing arrangement. We are also honoured by the presence of some thirteen Presidents, Vice-Presidents, or Chairmen of our sister scientific and technical organizations. I shall rapidly read their names, but they must all feel assured that they are very welcome here today. Firstly, one of our own Past Presidents and members, Mr Geoff Goode in his capacity as President of the Associated Scientific and Technical Societies of South Africa; Mr L. R. Robinson, President of the South African Institution of Mechanical Engineers, and Mrs Robinson; Mr G. Goedhals, President of the South African Institute of Electrical Engineers ; Dr Antrobus, President of the Geological Society of South Africa, and Mrs Antrobus; Mr T. V. Dean, Vice-President of the Institute of Land Surveyors of the Transvaal, and Mrs Dean; Mr R. M. Stroh, President of the Mine Ventilation Society of South Africa; Mr Ken Steele, President of the Association of Mine Managers, and Mrs Steele; Mr Mike Gericke, President of the South African Council for Professional Engineers; Mr R. G. Matthews, President of the Institute of Mine Surveyors of South Africa; Mr P. H. Pettifor, President of the Institute of Production Engineers, London, and Mrs Pettifor ; Dr Nico Stutterheim, Chairman of the South African Institute of Chemical Engineers, and Mrs Stutterheim; Professor F. A. van Duuren, Chairman of the Engineers' Liaison Committee in Pretoria; also, I haven't spotted him but I trust he is here-Mr Alex Bain, who is Chairman of this Institute's Witbank/Middelburg Branch. To one and all, ladies and gentlemen, a hearty word of welcome. Not last on our list, a word of welcome to Mr Eric Boden, the Manager of A.S. and T.S. We also have with us I trust, Dr Deist, and his good lady-Dr Deist will be figuring in our proceedings later this afternoon. Also Mr Barcza and Mrs Barcza. Mr Bareza, a former President of the Institute, also has a task to perform. Then, I hope two of our student prize winners are here-Mr Beetge and Mr Painting. Then we also have Mr Roberts, who is welcome in his capacity as co-author with Dr Deist. Then, last of all, a hearty word of welcome to Dr Helen Glen (I am not sure whether she has arrived yet, but she is certainly due to come)-the new Honorary Editor of the Institute's Journal. MEMBERSHIP The President: I have pleasure in announcing that, their names having been published in accordance with By-law 5.2.2, the following have been elected by Council to membership in the following grades Fellows: W. G. Jayes and F. K. Wright Members: D. W. Penman, A. W. Bryson, and D. L. Gibbs Graduates: R. J. Adey, J. P. Bond, R. C. Dunne, G. M. Entwhistle, J. M. Rendu, J. P. S. Turner, and A. P. van Jaarsveld Associates: A. Ellis, B. R. Hambly, A. J. Johansen, and G. W. Tregoning

Jan 10, 1973

Colloquium and General Meeting were held at Kelvin House on 19th May, 1971, the theme being 'Modern trends in coal mining practice.' Mr V. C. Robinson (President) was in the Chair. The Colloquium was attended by 205 delegates and was opened by the President at 9 a.m. OBITUARY The President: 'It is my sad duty to announce the death of C. C. Cullen, Fellow, who joined the Institute in 1946 and passed away on 15th March, 1971. As a mark of respect to the memory of the deceased and in sympathy with the bereaved I would ask you all to rise and observe a few moments silence'. ELECTION OF SCRUTINEERS The President: 'In terms of Clause 9.4 of the By-Laws I now call for the nomination of seven Corporate Members to act as scrutineers of the ballot for Council'. Messrs V. C. Robinson, Prof D. D. Howat, Dr J P Hugo, D. G. Maxwell, J. K. E. Douglas, R. J. Adamson and P. Lambooy were nominated by P. W. J. van Rensburg and seconded by P. A. von Wietligh. The President: 'Are there any further nominations? If not I declare these gentlemen elected.' MEMBERSHIP The President: 'I have much pleasure in announcing that the names of candidates, having been published in accordance with By-Law 5.2.2, Council has elected them to membership of the Institute in the following grades: Members: Douglas Edward King, Bryan Rudolph Scott, James Gregor Phimister, Anthony David Walters. Graduates: Cornelius Johann Muller, Marthinus Stephanus Mulder. Associates: John George Everson, Colin Robert Llewellyn Davies. Students: Francois George Enslin Beetge, Ewald Boshoff, Christiaan J. Cloete, Christopher John Davies, Cameron George Elvin, Kenneth Eric Field, Johannes Louis Fourie, Hans Gert Gastrow, Peter John Ledger, James Robert William Lindsay, Kynaston Lloyd McDonald, Richard Peter Mohring, Arthur Leslie Painting, Matthias Arthur Pascall, Ian Neil Sinclair, Donald Allan James Ross-Watt. MEMBERS TRANSFERRED TO A HIGHER GRADE From Member to Fellow: Peter Norman Roberts. From Associate to Graduate: Alfred Eric WaIter Fletcher. From Student to Graduate: Wilfried Pierre de Villiers, Edward Emile Eichenberger, William Alan Nairn, Lodewyk Johannes de Jager, Colin Henry Obray, John Grenig Rees. COLLOQUIUM The President opened the proceedings and introduced Mr N. W. S. Schumann as the overall chairman for the day. The following papers and contributions were presented: FIRST SESSION: Chairman R. C. J. GOODE. Paper: 'Problems encountered in the operation of a new colliery' by P. M. C. Wilson and A. A. Oakes. Contributors: D. J. Moloney, G. R. Canny, I. G. Evans, R. B. MacGillivray, Dr F. G. J. de Jager, M. J. Deats, and N. Zolezzi. R. B. MacGillivray Mr President and gentlemen, I would like to congratulate the authors on presenting a most interesting paper on a very important subject. After several attempts at finding suitable reserves to extend the life of Welgedacht Exploration Company's Utrecht Colliery a block of coal rights was acquired south west of the town of Utrecht. A study of these reserves showed that they would enable a satisfactory return on capital invested to be achieved. It was decided therefore to open up what is now called the Zimbutu section of Welgedacht Exploration Company, to produce 41 000 metric tons of coal per month. The decision to open this section was taken in August, 1968 and due to certain allocation requirements it was necessary to bring it into production by the 1st of January, 1970. Fortunately a fair amount of statistical data had been collected prior to August, 1968 from the old Utrecht Colliery in anticipation of opening a mine and a fairly detailed rechnical report had been prepared. As a result the dead line was only missed by four days. Main features of the Design A feasibility study was carried out on three possible shaft positions and the final position was selected from these three on economic grounds. As the coal seam at the selected shaft position was only 21 metres below the surface it was decided to sink two twin incline shafts to enable rapid establishment of through ventilation and alternative hauling arrangements for quick development. This also allowed the final vertical ventilation shaft to be placed at some distance away to avoid the nuisance of fan noise. Second outlet requirements are also very well met by these twin inclines. Again on the basis of economics and also due to the uncertainty of roof conditions it was decided to use hand loading methods underground. However, to allow for future possible conversion to mechanised loading, should this become economical through rising wages, a conveyor belt was installed in the hauling shaft. This conveyor belt is fed from an endless rope haulage in the east companion by means of tipplers, a bin and a feeder. The main development heading was left clear for the future installation of a conveyor belt which would afford easy conversion to mechanisation.

By R. S. J. Toit

Discussion: T. L. Gibbs,* (Honorary Vice-President and Fellow): In terms of the Pneumoconiosis Compensation Act of 1962, a Pneumoconiosis Risk Committee was established whose function it is to estimate (by whatever means the committee deems fit) in respect of every controlled mine the pneumoconiosis risk to which persons employed in a dusty atmosphere at that mine are exposed. In estimating such risk the committee may estimate different risks in respect of individual mines or parts of mines or classes or groups of mines or occupations or localities at mines. The pneumoconiosis risk may be reviewed and re-estimated at any time. The Act provides further that the General Council for Pneumoconiosis Compensation shall apportion the levy imposed on owners of controlled mines on the basis of the pneumoconiosis risk determined by the risk committee and the numbers of persons employed in a dusty atmosphere. The task of the risk committee is a most responsible one and also a very difficult and complex one in view of the many different types of mines, rock formations, dust conditions, etc. Quite obviously, comparisons between mines cannot be made on dust concentrations alone as different mineral dusts have different toxicity or pneumoconiosis response factors. However, with its present knowledge, the risk committee is satisfied that the risk at mines, other than coal mines, is related to the mean quartz-equivalent dust concentration to which persons are exposed and the estimation of risks is based on this relationship. From the above, it will be clear that the work done by Dr du Toit on the problem of basing the current rate of levies to provide for pneumoconiosis compensation on the current dust hazard at mines has been of immense value to the risk committee. Up to now the risk committee has not been able to obtain complete and accurate information on the dust exposure of persons at all mines - and, in fact, it is doubtful whether it will be economic or practicable to obtain this in the foreseeable future - but reasonable assessments have been possible from routine dust sampling in some cases and from periodic comprehensive dust surveys in others. As a temporary measure the risks of some mines were estimated initially on a group basis relating to average dust conditions and the type of rock and mineral mined, but as more information became available, differentiation between individual mines became possible. It is the aim of the risk committee to eventually apply such a differentiation in all cases and to ensure that within the bounds of practicability each mine pays for its risk and for its risk only. In this connection, the relationship between the levies and the amounts actually paid out in compensation are examined regularly. In conclusion, I wish to add my congratulations to the author on his excellent paper. His findings will assist materially in the just administration of that very important piece of beneficial legislation, the Pneumoconiosis Compensation Act. G. K. Sluis Cremer MD (Visitor): Dr du Toit has made a valiant attempt to relate dust hazard and the rate of collecting funds for the purpose of paying compensation for Pneumoconiosis. In doing so he has had to make a number of assumptious, some of which touch on the medical aspects of pneumoconiosis. It is worth discussing whether these assumptions are justifiable. Pneumoconiosis is defined in our Pneumoconiosis Act as permanent disease of the cardio-respiratory organs which is caused by the inhalation of mineral dust. To a non-medical person this definition has probably a clear cut meaning. The doctors however have to deal with such conditions as silicosis and asbestosis where there is a well defined dose response relationship to the inhalation of quartz and asbestos respectively and on the other hand chronic bronchitis where the relationship to dust inhalation is poorly defined and where certainly no clear dose response relationship has emerged after many investigations in this country and overseas. Nevertheless since 1953 about half of our certifications for Pneumoconiosis are on the grounds of chronic bronchitis i.e. the X-rays show no evidence of silicosis, asbestosis or other relevant disease. This fact must affect Dr du Toit's computations. The next assumption we should examine is the manner in which toxicity factors have been allocated to the various mineral species. These allocations have in part been based on a restricted number of animal experiments carried out overseas but mostly in South Africa by Webster at the Pneumoconiosis Research Unit. To extrapolate the findings in a relatively small number of animal experiments to the expected reactious in man is a notoriously dangerous exercise. Furthermore the bracketing together of all silicates (except asbestos) and the insoluble metal oxides is entirely unacceptable. Talc (a hydrated silicate of magnesium) and muscovite mica (a silicate of aluminium and potassium) cause pneumoconiosis in their own right. On the other hand

Jan 3, 1970

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins' calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann's constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,' the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously' and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.' It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3' of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:' basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,'-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6'7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5' of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969