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By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature' not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953

By S. R. Bardsley, S. T. Algermissen

Induction, nuclear and sonic well-logging methods were employed in a Green River formation oil-shale analysis and evaluation study conducted in northeastern Uintah County, Utah. The physical and chemical properties of an oil-shale section, previously cored and assayed by conventional methods, were used to evaluate the response of the various logs. The logging program was designed to measure variable properties of oil shale which relate to oil-yield potential in order that a relationship between assay-oil yield and log-determined properties could be identified, thereby permitting a direct determination of yield potential from logs alone. All of the major oil-shale zones and section ttlarkers are recognizable on the logs used in the study. The relationship between the response of the Density and Sonic logs and the assay-oil yield in gallons per ton was suficient to perinit the derivation of equations expressing the relationships. These equations can be used to determine the potential oil yield in gallons per ton of an oil-shale zone or section. The Neutron log response distinguishes the rich oil-shale intervals from the lean intervals, but does not appear to permit establishment of a quantitative relationship. The Garnma-Ray and Induction logs indicate only a qualitative relationship to oil-shale yields. Logging oil shale by Gamma-Gamrna Density and/ or Sonic logging methods will permit a fast, economical and accurate means of evaluating the potential yield of oil-shale deposits. Considerable sums of money have been allocated to Green River formation oil-shale evaluation during the past years by both private enterprise and Federal and state governments. The result of the work accomplished to date is commendable, but the task of fully exploring and evaluating one of the world's greatest reserves of potential energy for economical exploitation is enormous and much information is still needed. Present methods of evaluation consist primarily of sampling and assaying the oil shale for potential yield. The data received are excellent, but are both costly (inasmuch as it requires funds specifically allocated for the evaluation purpose) and time-consuming (as each representative sample must be assayed in the laboratory by specially trained personnel). At the present time, the Green River formation oil-shale province is one of the most active areas in the Rocky Mountain region for exploratory oil and gas drilling. This activity could play a twofold role and serve the function of spear-heading many oil-shale evaluation programs, as it could provide both cutting samples for assaying, geophysical data and modern well logs. This paper deals with a recent study conducted on Green River formation oil shale in which the application of induction, sonic and nuclear well logs to oil-shale evaluation was tested and proved. THEORY AND DEFINITIONS Oil shale may be described as siliceous marlstone, rich in solid organic matter called "kerogen". Kerogen is only slightly soluble in organic solvents, but it will decompose and yield oil vapors and gas when heated to destructive distillation temperatures at about 800 F. The mineral constituents of Green River formation oil shale are found in essentially uniform proportions with one another. The dominant types are, in the general order of abundance, dolomite, calcite, feldspars and quartz. Kerogen is also essentially uniform in its composition, and is about 80 per cent carbon and 10 per cent hydrogen by weight. The ratio of kerogen to the mineral constituents determines the richness or potential yield of the oil shale. This ratio also determines the total physical and chemical properties of the rock and provides a basis by which oil-shale richness may be determined from well logs. Because Green River formation oil shale was deposited in a lacustrine environment, the lithology is laterally consistent over wide areas. The vertical section consists predominantly of thin bands of alternating rich and lean oil shale which have been described by Bradley' as varves. The varves are occasionally broken by thin bands of volcanic ash and tuff and by zones of lean vugular oil shale. The effect that the thin non-oil shale beds and vugular zones would have on the well log analysis was a prime concern in the study. To cope with this possible problem, the logs used in the study were of two types: (1) logs believed to respond favorably to those properties of oil shale which are dependent upon the kero-gen-to-mineral ratio, these logs being the Gamma-Gamma Density log, the Sonic log and the Neutron log; and (2) logs that would respond to litho-logies and properties within the oil-shale section not associated with yield that might result in anomalous responses by the yield-measuring logs. Logs of the second type were the Gamma-Kay log, the Induction log and the Caliper log. THE PRESENT STUDY The present logging study was con-

By J. W. Edington

THE Hopkinson bar has become a popular technique for the measurement of the mechanical properties of materials deformed at high strain rate. Maximum use of the equipment is made in the arrangement first used by Kolskyl in which a short compression specimen is sandwiched between two pressure bars and is loaded by a single pulse travelling through the system. The pressure bars are used both to apply the load to the specimen and as transducers to obtain continuous strain-time histories of three pulses, incident on, reflected, and transmitted by the specimen. The data measured by the pressure bars can be analyzed in terms of the stress/strain behavior of the specimen.2'3 However, one of the assumptions of the analysis of the observed pulses is that the total stress and total strain do not vary significantly from point to point within the specimen at any given instant during the deformation process. Although this assumption is generally justified for very short disc-like specimens2 the situation is uncertain for larger specimens. For example, at small plastic strains (-0.01) Hauser et al.2 have some evidence of small flucations in the total stress within the crystal during deformation, even in relatively short aluminum specimens. In addition, Karnes4 has shown that the plastic strain, and by inference strain rate, is different at each end of a compression specimen tested in a Hopkinson bar, although the length of the specimen was not specified. Recently, the mechanical properties and the dislocation substructure have been investigated in single crystals of columbium5 (length 0.25 in., diam 0.19 in.), and copper6 (length 0.5 in., diam 0.5 in.) deformed at high strain rates. As part of this research program the assumption that the plastic strain is constant throughout the specimen has been checked by measuring the total dislocation density as a function of position in the specimen. Compression specimens of the same orientations and dimensions were tested as described previously5,6 sing a split Hopkinson bar. Since any discontinuity in strain distribution is most likely to arise during the initial stages of deformation the investigation was performed on specimens deformed to plastic shear strains of 0.054 (copper) at a strain rate 1.2 x l03 sec-1, and 0.06 (columbium) at a strain rate 1.5 X l03 sec-1. The orientation of the single crystals is shown in Figs. 1 and 3. Thin foils were taken parallel to the most highly stressed slip plane, i.e., (111) in copper and (011) in columbium, using conventional disc techniques. The dislocation densities were measured using first order reflections with compensation for invisible dislocations.5'6 In the copper single crystals the discs were randomly distributed throughout the cross section of the specimen. However, the dislocation density obtained from each disc was plotted vs the disc positions relative to the ends of the specimen. The results for the copper specimens are shown in Fig. 1. Clearly the dislocation density is constant throughout the main portion of specimen within the experimental error. The error bars on the dislocation densities correspond to a shear strain variation of 0.015 on the basis of previous measurements% ± of the rate of increase of dislocation density with strain in copper single crystals of the same geometry. Thus within this experimental error the plastic strain can be concluded to be constant within the specimen and the assumptions used in the analysis of the stress/time curves are therefore reasonably valid. The higher measured dslocation density near the impact end and the lower dislocation density at the bar end of the copper specimen is in agreement with the results of Karnes4 who showed that this strain/time curve rose to a maximum more rapidly at the impact end compared with the bar end. Hauser et al.2 have also pointed out that at small plastic strains (-0.01) the strain at the impact end of the specimen may be greater than that at the bar end. Thin foils taken from different points within the columbium single crystals demonstrated that the dislocation density could vary significantly within the specimen, see Fig. 2. Large areas of some thin foils up to 30 µ sq contained very few dislocations, see Fig. 2(a). However, in other parts of the compression specimen dislocation configurations like those shown in Fig. 2(b) existed over large areas (-30 µ sq). As a result, when the average dislocation density in a thin foil is plotted as a function of the position of the thin foil relative to the ends of the specimen, considerable scatter is observed, see Fig. 3. In this material then, the local dislocation density, and consequently the

Jan 1, 1970

This surveillance report summarizes data on work-related fatal and nonfatal injuries, illnesses, and hazardous exposures in the mining industry for the 10-year period 1986-1995. The term "surveillance," as used in public health, may be new to many readers of this report. With regard to occupational safety and health, the goal of surveillance is to describe the occurrence of work-related injuries, illnesses, and known hazardous exposures; to identify new hazards that may occur due to the introduction of new technology or other factors; and to assess the effects of preventive measures designed to improve worker safety and health. Surveillance provides an overall picture, which can be used to focus resources on areas most in need of prevention programs or further research. Surveillance generally requires the use of multiple sources of data, all of which have their own strengths and limitations. Surveillance in the U. S. mining industry is complicated by the fact that U.S. national data systems that provide information on mining are based on two different definitions of the mining industry. One is established by the Mine Safety and Health Administration (MSHA), the other by the Standard Industrial Classification (SIC) System [Office of Management and Budget 1987] and the 1980 U. S. Bureau of the Census (BOC) Classification System [U.S. Bureau of the Census 1982]. The mining industry as defined by MSHA is based on the regulatory jurisdiction of that agency. Reporting requirements for injuries, illnesses, and workplace exposures are stipulated under the Federal Coal Mine Health and Safety Act of 1969 and the Federal Mine Safety and Health Amendments Act of 1977. Of note is that the oil and gas extraction industry falls outside of MSHA jurisdiction. The Occupational Safety and Health Administration (OSHA) was charged with enforcement in the oil and gas industry under the Occupational Safety and Health Act of 1970. Under the SIC, the definition of mining covers the extraction of naturally occurring minerals, including liquids (petroleum), gases (natural gas) and solids (coal, metal, and nonmetallic minerals). Exploration and development of mineral properties are also included in the SIC definition of the mining industry. The SIC was developed by the Office of Management and Budget for use in classifying establishments based on the type of economic activity in which they are engaged and serves as the industry classification standard for all establishment based Federal economic statistics. This classification is important for occupational safety and health surveillance because it also serves as the industry classification system for all data on work-related injuries and illnesses collected by the U.S. Bureau of Labor Statistics (BLS). The U.S. Bureau of the Census uses an industry coding scheme similar to that used by the SIC. For the mining industry, the categorization is identical in both systems. Death certificate data made available by the National Center for Health Statistics (NCHS) are categorized under this system. Death certificate data are particularly important for surveillance of mortality from work-related illnesses. Key differences between the SIC/BOC categorization system and the MSHA system can be summarized as follows: • MSHA excludes the oil and gas industry, which is classified as part of the mining industry under SIC/BOC. • MSHA excludes work that is done off of mine property; work off of mine property is included under SIC/BOC if it is performed by an establishment falling into one of the SIC/BOC mining industry codes. • MSHA includes mine-associated mills and processing plants; these are classified under the manufacturing industry, rather than mining, according to the SIC/BOC coding structure. Since the data collected by MSHA and the data collected by BLS and NCHS using the SIC/BOC classification system are both important sources of information on the mining industry and in many cases serve different purposes, data from both systems are presented in this report. In general, data using the SIC/BOC system are comparable across U.S. industries and should be used when comparing mining to other U.S. industries. Much of the data in this report are presented in the form of frequencies or rates. A frequency provides only a count of the number of cases without providing any information about the risk of occurrence. Rates provide an estimate of the risk of injury or illness. The reader is cautioned, however, that rates based on small numbers can be unstable; thus, any inferences should be drawn with care. In this report, no rates are presented for groups in which there were fewer than three cases. The incidence of most injury and illness conditions differs by age, sex, and race. For this reason, data in many surveillance reports are adjusted for these demographic factors. It was not possible to do this for most of the rates in this report because information on demographics was not available. With the exception of the proportionate mortality ratios (PMRs), all data presented are unadjusted. A detailed account of the sources of data is in appendix A. The methods used in data selection and analysis are described in appendix B.

Jan 5, 2000

By VAN. H. MANNING

During the nine years that have elapsed since the Bureau of Mines was established in 1910, the work of the bureau has included many investigations that have proved of high value to the Nation. Eleven mining experiment stations established by act of Congress have greatly increased the bureau's usefulness; being situated in the mining fields, these stations are closely in touch with industrial needs, and the results of their research and educational work are more directly available to those engaged in the mining, metallurgical, and mineral industries. In the United States mining is second in importance to agriculture only. The Federal Government annually appropriates large sums in the interest of agriculture, whereas the appropriations for mining are relatively small. But the nation-wide popularity of Government assistance to agriculture should not overshadow the need of Federal assistance to the mineral industry. With scientific management farms can be made to produce indefinitely without any depletion of the potential resources of the soil, but the mineral wealth of a country is a fixed quantity, and every year's production brings nearer its ulti- mate exhaustion. As the deposits of the richer or more readily available ores, espe- cially those in the West, have been depleted, development of methods for mining and treating the leaner or more inaccessible ores has lagged, so that meeting the increasing demands for certain metals is becoming more and more difficult. In some branches of mining the small inde- pendent operator is greatly handicapped. He has to rely on custom mills and smelters for the profit or loss of his product, and because of relatively inefficient methods of milling or smelting he may receive no return for much of the ore he mines. Even though the small operator thinks he knows of improved methods of obtaining the metals from the ores, he can not afford to install the necessary machinery or to carry on experiments that may or may not prove successful. In view of the increasing need of metals and the impossibility of renewing the ore supplies, efforts should be directed toward developing the most economical and efficient methods in mining and metal- lurgy. The great mining companies carry on independent research work, some of them on a large scale; but as such work is usually undertaken for gainful purposes, these companies do not feel under any obligation to give the results of their investigations to the world. Clearly the solution of the difficulty is to place in the mining districts trained mining and metallurgical engineers who will investigate and solve the problems for the benefit of the whole industry. It is with this purpose in view that experiment stations of the Bureau of Mines have been established to investigate economy, efficiency, and safety in mining, and to make public the results of the investigations. The Federal Government can be of most help in developing the mineral resources of the country when its forces are brought in direct contact with these resources. Mining is as old as civilization, but only within a generation has this country busied itself with any other problem of mining than the amount of mineral products that could be put upon the market. Little concern was felt if much of the metal in an ore was wasted, if the miner lived in unsanitary surround- ings and died of preventable disease, or if accidents occurred fre- quently and from causes that could easily be controlled. Now we realize that the waste of any resource is inexcusable. The mineral wealth of the country can be mined but once. The task before the Nation is to recover as much metal as possible from the ore in the ground, and to do this in the most economical way without waste of human life. This task is of such magnitude as to warrant aid from the Government through experiment stations. In its efforts to make the work of these stations of most benefit to the mineral industry the Bureau of Mines seeks the cooperation of State authorities, of mine operators, of miners' organizations, and of every person interested. These experiment stations also serve an educational purpose. Gen- erally speaking, mining is not a preferred occupation. The miner should have reason to take greater interest in his work; he should feel that the experiments the Government is making affect him vitally by enabling him to increase his production and by making his work safer. The mine operator should realize that the Government stands ready to aid him, and he should know that he can bring his own problems to a Government organization that is trained and equipped to solve them. The surest method of accomplishing these results is to carry the work of the Bureau of Mines into the mining regions through the establishment of experiment stations easily accessible both to the mine operator and to the miner. Many miners in this country do not read English, but they can understand motion pictures of mining methods; they can learn how lives can be saved in case of accident; and they can appreciate the larger results gained by modern methods and equipment. In every

Jan 1, 1919

By Jacques H. Nantel, James F. Archibald

"Frozen tailings material may be required, in the future, to perform the support functions of underground backfill in mines located in zones of permafrost, notably in the high Arctic. To date, no knowledge of physical support parameters of such materials has been obtained in Canada due to the limited mining activity in permafrost regions. It is therefore judged essential that the important physical and mechanical properties relating to frozen tailings material be assessed.Innovative mining methods will be required to cope with the harsh environmental conditions that exist at mining sites in the Canadian Arctic. A preliminary laboratory study, in the absence of field trials at limited Arctic mining sites, has been completed in which the physical and mechanical properties of several types of representative mill tailings mixtures have been investigated. A variety of tests, to determine frozen slurry and pelletized tailings strength properties, moduli of compression, optimum water contents, deformation characteristics and the like, have been conducted.The results of this study will be used to establish guidelines for the suitability of tailings use in such northern mining environments. IntroductionFrozen tailings material has never been used to backfill underground openings in Canadian mines. At present only one Canadian mine, the Polaris Mine situated on Little Cornwallis Island, is investigating the use of frozen backfill. However, the Canadian North covers a large territory and potentially contains a large number of mineral deposits. The understanding of concepts related to mining activities in sub-zero frozen ground is therefore important.The implications of using frozen tailings as underground backfill material are far reaching both from the point of view of mine stability and disposal of tailings in the arctic regions.The strength of frozen materials (soil, backfill, etc.) may take on different meaning depending on the engineering situation. Both the concepts of rupture and excessive deformation need to be considered.The functions usually required to be performed by the backfill material in underground mines may be summarized asfollows:a) working floors; such as in cut-and-fill stopesb) stope wall support; for cut-and-fill and delayed fill stope~c) self-support when backfill is exposed on one face; during pillar recovery phases.For fill functions such as working floors, the short-term response of the frozen fill is the dominant concern. For the other fill functions, the long-term deformation response of the frozen fill, or creep, is of interest."

Jan 1, 1986

By Charles Austin

IT has been known for several years1 that certain alloys of the Konal type, containing commercial cobalt (99.32 per cent C0 and 0.42 per cent Ni) and varying amounts of ferrotitanium, exhibit very high tensile strengths at 600°C. However, their pro-portional limits and yield points are rela-tively low. Published data1 for the alloys quenched in water from 950°C. and then tested at 600°C. are summarized in the upper section of Fig. I. Similar specimens that were aged at 650°C. for 72 hr., after quench and prior to testing at 600°C., gave the results shown in the lower section of Fig. I. TABLE I.-Analysis of Material I Percentages Constituent Sample Sample Sample 3125 3124 3123 Si 0.25 0.51 o.6o Fe 4.15 10.70 13.17 Ti I.15 3.58 4.70 Mn 0.30 0.41 0.42 Co (by difference)^ 94.15 84.80 81.71 The cobalt from all three samples, united and tested for nickel, gave 0.54 per cent Ni based on the weight of cobalt. In the present work the investigation of the properties of these materials has been extended by a study of the tensile deforma- tion characteristics in moderately long-time tests at 600°, 700° and 800°C. after quenching from various solution tempera-tures. In addition, some metallographic studies have been made to correlate with the deformation tests, and to obtain in- FIG. 1.-EFFECT OF VARYING AMOUNTS OF FERROTITANIUM (FE2TI) ON PHYSICAL PROPER-TIES OF COMMERCIAL COBALT. (C. R. Austin.1) Upper section. Tested at 600°C. after water-quenching from 950°C. Lower section. Tested at 600°C. after water-quenching from 950°C. and aging 72 hr. at 650°C. FIG. 2.-PORTION OF QUASI-BINARY DIAGRAM COBALT-FE2TI AS DETERMINED METALLOGRAPH-ICALLY. formation on the quasi-binary system Cobalt-Fe2Ti. The material, very kindly furnished by the Westinghouse Electric and Manufac-turing Co. in the form of hot-swaged rods of 3/16-in. diameter, analyzed as shown in Table I. The alloys, when originally made up,1 were based upon an iron-titanium com-pound, Fe3Ti, as indicated by the work of

Jan 1, 1940

By T. C. Phalen

"Necessary Qualities There mines are located in out of the way places, where timber is scarce and its price high, the problem of protecting it from fire risk is of considerable practical importance. Scarcity of timber for mining purposes is commonly met with in the more arid parts of the country, where, also, mine timbers are most likely to become dry, and inflammable, and where, therefore, the risk from fire is accentuated. Any effective and cheap method of securing adequate protection of such timber at the lowest possible cost is worthy of careful investigation. The use of magnesite cement has been suggested in this connection.The necessary qualities for any substance for the use suggested above may be summarized as follows: It should be resistant to abrasion, and to impact and structural stresses. It should be durable when subjected to the action of the ele¬ments, and stable to any minor derangements of the base on which it is placed. It must be relatively unaffected by changes in temperature, by the action of water, and should adhere to the material on which it is placed, and it should also be free from shrinkage cracks due to setting up the material, Magnesite cement appears to fulfill the various conditions outlined above.The elasticity of such cement is the outstanding quality which makes it desirable for exterior work. It also possesses the ability to adhere to all materials in a marked degree. Its freedom from expansion and contraction after setting is one of the principal reasons for its adhesive quality. It may be applied to old brick or stone walls, even tho they have been repeatedly covered with paint, and the quality of ad-hearing to wood makes it possible to secure a weather-proof protection to the wooden casings and trim of exterior openings. The quality of adhesion and elasticity is easily proved by applying a 1/2"" layer to a 1"" board which has been first covered with metal lath. Such a board, about 8 feet long, may be repeatedly deflected about 3"" in the center without breaking the bond to the board, or causing any cracks to appear in the magnesia cement. The ability to resist fire as well as the possession of insulating qualities are also desirable characteristics of magnesia cement stucco."

Dec 1, 1919

By B. P. Watson

Uniaxial tests performed on core from instrumented sites at Amandelbult 1 shaft, Impala 10 shaft and Union Section Spud shaft showed a nonlinear elastic relationship between applied load and induced deformation. This nonlinear behaviour does not appear to be dependent on borehole orientation but in the case of the Amandelbult and Union sites appears to have been influenced by the stress condition of the rock mass at the time of drilling. Cores drilled at these two sites under destressed conditions, such as over a stope, showed a linear elastic response to the applied load whereas most of the cores drilled under relatively high radial stresses were nonlinear. The Impala 10 shaft tests, however, all showed strong nonlinear behaviour irrespective of the stress condition of the rock mass at the time of drilling, although high stress conditions may have influenced the severity of the nonlinearity. A comparison between underground stress change measurements and an elastic model indicated that the rock mass became nonlinear when the virgin stress condition was relaxed to about 10 MPa. The cores for laboratory testing were retrieved from vertical boreholes drilled up from the centre of a stope and from horizontal boreholes drilled over pillars and stopes at about 600 m, 1 100 m and 1 400 m below surface for the three sites respectively. The k-ratios under virgin conditions were estimated from sockets, modelling and stress measurements to be 1.0, 1.3, and 0.5 for the Amandelbult, Impala and Union sites respectively. Of the three sites, therefore, Impala 10 shaft appears to have had the highest virgin stress state. Tests performed on similar rocks from shallower depths at Impala Platinum essentially showed a linear relationship between stress and strain. From the small Impala Platinum rock test database available to the project, it appears that the nonlinear elastic behaviour initiates at this mine from about 1 000 m below surface and seems to become progressively more nonlinear below this depth. In addition, the nonlinear elastic rocks are weaker, have a lower Young?s modulus and a higher Poisson?s ratio than their linear elastic equivalents. Interestingly the tangential Poisson?s ratios of the nonlinear elastic materials are often greater than 0.5 at 50% of the failure stress, suggesting an early failure initiation. The paper describes the microscope and modelling work done to determine the causes of the nonlinear behaviour and discusses some implications of the behaviour for deep-level mining.

Jan 1, 2009

By S. H. Lucas

"This paper describes the development and application of single-stage fluidized bed continuous ion exchange to the following processes: removal of base metals from mine water; cyanide removal from gold mill waste; uranium removal from sulphuric acid leach liquor; and uranium removal from mine water. IntroductionThe recovery of metals by fixed bed ion exchange has been practiced for many years. However, the operation has been semi-continuous and can only treat clarified liquors. Substantial savings could be made if the operation were continuous, thus reducing the resin inventory, and if the costly filtration and clarification steps could be eliminated. Work has been in progress over the past twenty-five years on the recovery of metals from unfiltered ore leach slurries, heap leach liquors and mine drainage waters containing a small amount of suspended solids. In the case of dilute waste solutions, with suspended matter and high flow rates, filtration is usually prohibitively expensive.Continuous ion exchange operation using fluidized beds has made it possible to reduce considerably the resin inventory and to allow the treatment of unclarified liquors and slurries. The subject has been reviewed on several occasions (1. 2. 3, 4). Although fluidized beds in multi-stage columns are an improvement over previous resin-in-pulp treatment, they have complicated internal structure and I or involved automatic control systems to move the resin stages.Slater and Prud'homme performed studies on multi-stage fluid beds, and concluded that the performance of single, deep fluidized beds of resin with continuous or semi-continuous flow of both phases would be worth investigating, particularly in the case of very dilute metal solutionsoi, A pilot plant was designed and built at CANMET in a cooperative project with Dr. Slateroi. The use of deep fluidized beds of resin (with a large height/diameter ratio) for treating dilute solutions has the attraction of engineering simplicity. Extreme simplicity of equipment design is considered of paramount importance when treating, for example, mine waters at high flow rates, possibly of the order of several million gallons per day. This paper describes the development of the concept of single-stage fluidized bed continuous ion exchange arid reviews the pilotplant development of processes for the treatment of base metal mine water, cyanide waste water, uranium leach liquor and uranium mine water."

Jan 1, 1980

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Thomas Barczak

Pumpable roof supports provide an alternative longwall tailgate roof support and have grown in usage during the past few years. Heintzmann Corporation has been installing pumpable roof supports at the RAG Resources Emerald Mine in western PA since 1998, where they have provided effective roof control in their longwall tailgates. Despite the success of these supports in this application, questions remain regarding critical design issues for optimizing the use of this support technology. The support loading profile is characterized by a high initial stiffness with peak loading occurring at less than one inch of convergence, followed by significant load shedding with a post failure capacity comparable to that of wood cribbing. Therefore, the key to optimizing the support utilization is to provide sufficient load density to prevent convergence from occurring beyond the peak loading capacity. This requires an understanding of how the supports interact with the ground conditions, hence measurement of the ground reaction curve. In order to obtain this information, pumpable roof supports were instrumented to measure support loading. Roof deformation and roof-to-floor convergence measurements in the vicinity of the instrumented supports were also made. The experimental parameters for the installation were the support spacing and water¬to-solids ratio of the grout, which controls the grout strength and ultimately the maximum capacity of the support. The study clearly shows that at this mine a 24-inch diameter support is fully capable of providing adequate ground control under depths of cover of 750 ft as only 50 pct of the available support capacity was utilized outby the longwall face. It was also shown that the 2.00 to 1 water¬solids ratio, despite providing a slightly softer support response, is sufficient for maintaining the same degree of roof control provided by the traditional 1.75 to 1 grout mix. The 10-ft spacing of the supports did not cause any ground control problems outby the face. However, inby the face the performance of the support is degraded once the peak capacity of the supports is exceeded. It appears that the large load shedding behavior, which is characteristic of this support following peak loading, allows the immediate roof to separate. When this happens, the support is unable to regain control of the roof in time to prevent failure of the immediate roof beam.

Jan 1, 2003

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Charles T. Malcomson

In the United States, improvements in methods of combustion have made possible the use of the smaller sizes of anthracite. This coal is now being reclaimed from the culm banks accumulated by the miners in the more prodigal years. To-day the freshly mined "slush" is segrega,ted and stored against the time when, through briquetting or some other means, it may be utilized as a commercial fuel. For many years Europe has achieved enviable results in the conservation of her small coal by briquetting. This profitable industry, first placed on a commercial basis in France in 1842, has grown to such magnitude that the production during 1913 exceeded 36,000,000 short tons. Briquets produced in Great Britain are used principally for steam purposes and the greater part of the output is either exported or taken by the Admiralty. On the Continent the briquets are sold in all branches of the coal trade. The French railways consume from 16 to 40 per cent. of their fuel in briquet form, and in Germany the lignite briquets (of which 20,000,000 tons were produced in 1913) are as familiar and interesting to the American traveler as the huge porcelain stoves in which they are burned. It is not strange, therefore, that aggressive and far-sighted promoters heralded this means of converting our ubiquitous coal waste into revenue. To the superficial student the briquetting process seemed so simple as to make success easy. It is for this reason principally that the path of the industry in America has been strewn with failures. The rash enthusiast had either not worked out the mechanical problems involved or had failed to grasp the local conditions under which the briquets must be made and sold. It may be confidently stated, however, that in spite of the many vicissitudes through which it has passed, coal briquetting is now an accomplished economic success in this country, and as a profitable adjunct to the coal industry it has come to stay. Several valuable contributions relating to coal briquetting are found in the Transactions. Charles Dorrance, Jr., has sketched briefly the history of the anthracite briquetting plants from the time of Loiseau's pioneer plant down to that of the Lehigh Coal & Navigation Co. at Lans-ford. Since then this phase of the industry has remained practically at

Jan 1, 1915

By Frank W. Harris

The strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chcniical and physical considerations, t,he high conductivity required for copper wire in the clcc-trical industry generally precludes the possibility of obt,aining tensile strength through the use of alloys. Consequently, this strenglh is largely a rnatter of the ~hysical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., arc matters of prime importance. The experiments described here have becn carried out dl~ring the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigat,ion of sorne of the questions mentioned above, with the object of studying thc physical ~t~ructure of hard drawn copper wire and the influence of ccrtain factors on t,hat st'ruct.ure. The work has been of an exploratory nature, rather than con~prehensivc., but it was thought that the result,s might prove of sr~fficient general interest tjo warrant their publicatlion. The bulk of the hard drawn coppcr wire used in places where strength is an important factor is rnanufacturcd to strict specification, based USU-ally in the United States on thab of t,he Arrlerican Society for Tcst'ing Materials (B-1-23). This specification calls for almost as high a, valuc of t,ensilc strength, consistent with elongation, as it is possible pract'icnlly to obtain, and only physically perfect mlaterial can be relied on to lliect such a specification. Obvious defects, such as laminat'ions protluc:etl through fins in bhe original rods or brittleness duo lo ovt~rdrawing, arc. usually recognized and need only passing refercncc. Laminatlions can be detected by twisting and untwisting the wircx several times; they will show up on the surface in the form of fins. Pig. 1 shows a very bad example of this defect. Thc wire may bc perfectly smooth before twisting hut, when such larrlinations arc3 prcstmt they will readily show up under this treatrncnt. This trouble is caliscd by sirriilar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which thc wire in Fig. 1 was drawn.

By Axel Hultgren, B. Herrlander

THE original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between At and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880° was free from veining. Bannister and Jones4 considered veining in ferrite to be a manifestation of microscopical and submicroscopical inclusions. Northcott,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berglund. Tritton (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling.

Jan 1, 1946

By J. E. Graham, A. H. Glenn

Oil operators engaged in drilling on the Continental Shelf of Louisiana and Texas are in agreement that adverse weather and wave action are two of the greatest hazards to the safety and efficiency of their work. It was ami-pated when the offshore operations commenced that such would be the case, and experience to date has verified this assumption. Because atmospheric conditions and wave action involve tremendous amounts of energy it is highly unlikely that it will be possible to control any but the most localized weather and wave phenomena within the foreseeable future. Thus. as long as the offshore operations involve the movement of small craft and barges over exposed waters, and the transfer of personnel and heavy equipment from these craft to either fixed structures or larger craft at close quarters, the weather and wave problem will remain. Taking into consideration the persistence of the wave and weather problem and the improbability of achieving a direct solution, the Humble Oil & Refining Company, in planning its offshore campaign investigated the possibility of forecasting wave and weather conditions in order to provide warnings of dangerous conditions and increase efficiency in day-to-day planning of work. It was recognized that predictions of wave and weather conditions based on meteorology and oceanography, both geophysical sciences, are not 100 per cent accurate and application of forecasts in the offshore work was dependent on whether they provided information which was sufficiently greater in accuracy than the layman's guess to be worth the expenditure involved. During World War 11. meteorology and oceanography were used with success in reducing danger resulting from environmental conditions and increasing efficiency of operations exposed to the elements. This success was partially the result. of improvement in the scientific techniques involved and the procurement and distribution of observational data, and partially due to the large scope of the military operations which meant that a reduction of losses of a relatively small percentage of the total cost amounted to a large figure expressed in terms of dollars. Since the offshore drilling involves an extremely large financial investment, it was considered that the experience of the Armed Services in successfully employing meteorology and oceanography might be duplicated in the oil industry. In addition. the oil industry's successful experience in utilizing seismology, geology, and terrestrial magnetism; all geophysical sciences, indicated that meteorology and oceanography, also of the family of geophysical sciences and sharing their scientific assets and liabilities, might be profitably put to use. Since the immediate problem involving the sciences of meteorology and oceanography in the offshore campaign is wave action, a program was inaugurated within the Humble Oil & Refining Company during June 1947. the purpose of which was to ascertain the applicability and limitations of wave forecasting in the offshore campaign. A summary of the effective wave forecasting techniques developed during the war was prepared in the form of a forecasting manual for the Continental Shelf off Grand Isle, Louisiana, by Bates and Glenn. After completion of this manual, experimental forecasts were prepared daily over a two-month period by Graham and Thompson to determine the accuracy of the forecasts. It was considered that the accuracy of the experimental forecasts justified a more extensive test under actual operating conditions in the offshore work and the firm of A. H. Glenn and Associates was set up under the sponsorship of the Humble Oil & Refining Company to work with the Humble Grand Isle District in providing forecasts of wave and weather conditions over a one-year period. This paper discusses the service now provided to the Grand Isle District, its applicability and limitations. TYPE OF FORECASTS REQUIRED It was apparent before the commence-mence of the forecasting service that a specialized type of forecast was required. Many of the weather elements of interest to the general public, such as rain and temperature, are of minor concern to offshore operators. On the other hand, such elements as wave height and wind speed and direction are of great concern in the offshore operations since variations in wave height of a few feet in the critical range divide safe from hazardous working conditions. To be of utility. a forecasting service for the offshore work must provide detailed forecasts of the elements which affect the operation. With this in mind, it was decided that forecasts would include the following information: average wave heights to the nearest foot, wind speeds within a range of approximately 5 miles per hour, and wind directions within 221 degrees. Since the procedure for forecasting these elements involves thorough analysis of weather data, it was decided to include a generalized forecast of weather conditions such as rain and cloud cover, although these are of secondary importance.

Jan 1, 1949

By E. P. Burtchaell

A method is presented for evaluating the effect of gravity drive upon the reservoir performance of a high relief pool. Conventional forms of reservoir analysis do not consider the alterations in the basic material balance data caused by gravity segregation of reservoir fluids. A procedure is outlined for structurally weighting physical and chemical data for use in the material balance equation. It is demonstrated how actual pool performance data can be utilized to evaluate the future reservoir performance of a gravity drive pool. INTRODUCTION Conventional reservoir engineering. procedure is inadequate for the analysis of an oil pool which has considerable structural relief, steep dips, and good permeability development. In, pools of this type, gravity drainage has an important part in the movement of oil to the wells and the effects of gravity on the overall pool performance should be included in any analysis of reservoir behavior. Many engineers have the opinion that the force of gravity in the movement of oil is not important until the later life of a pool.' Probably the basis for this belief is that gravitational effects may not be readily discernible until a pool is nearing depletion. This would be especially true for pools not having a high degree of structural relief and permeability development. Actually the effects of gravitational forces are at a maximum when the pool pressure is high, for during this period the hydrostatic head of the oil column is at a maximum and the viscosity of the oil is at a minimum. Oil recoveries from pools having favorable gravity drive characteristics may equal or even exceed recoveries which might be expected from water displacement. Field evidence indicates that in some reservoirs gravity drive has resulted in recoveries greater than that which could have been expected from gas expansion or water drive.'.3 Unfortunately, the possible effects of gravity drive on pool performance have been underestimated and other reasons have been sought to explain the high recoveries obtained. There are unquestionably many reservoirs to which the principles of gravity drainage can be effectively applied. It is the purpose of this paper to illustrate one method whereby gravity drive is included in the reservoir analysis of an oil pool. A hypothetical pool, typical of many California reservoirs, is used as an example. As used in this paper, "gravity drive" is defined as the overall effect of gravitational influences on the recovery of petroleum from the reservoir; "gravitational segregation" as the gravity separation of oil and gas within the reservoir; and "gravity drainage" as the downward movement of oil as caused by the force of gravity. SAND VOLUME DATA Fig. 1 presents a structural contour map of the pool under study. Maximum closure is 1950 feet with dips on the south flank approaching 45". The original gas-oil interface was set at -5200 feet. Average thickness of the producing sand was 200 feet. For use in subsequent calculations ill this paper, the pool was subdivided into 100-foot vertical increments and the sand-volume content of each increment was obtained. If the gross sand thickness is small, under 100 feet, the sand-volume content can be obtained by superimposing an isopachous map upon a structural contour map and planimetering the average thickness of each 100-foot increment. For sand thicknesses over 100 feet, one approacli would be to construct a sufficient number of cross-sections of the pool from which the weighted sand-volume of each 100-foot increment could be obtained. Variations in the sand body with depth, as determined by core data, can also be included in the above process. Table I presents a summary of sand-volume calculations, core data, and the original distribution of reservoir hydrocarbons in the pool. Fig. 2 illustrates the structural distribution of the sand-volume content. A total of 171,398 acre-feet is contained within the productive limits of the pool. Assuming an average porosity of 25% and an interstitial water content of 20%, the original hydrocarbon content was computed to be 227,075,000 barrels. DEPTH-PRESSURE DATA The determination of the initial vertical pressure arrangement in the pool is necessary for PVT and material balance calculations. Whenever sufficient data are available, a plot of pressure versus subsea depth of measurement should be made. From this plot a representative fluid pressure gradient can be established. Lacking sufficient initial pressure data, an initial pressure gradient may he estimated or calculated from avail-

Jan 1, 1949

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By J. W. Rutter, K. T. Aust

The migration of individual, large-angle grain boundaries has been studied as a function of tempereature and solute concentration in specimens of zone i.e filled lead containig very small additions of silver and of gold. Tile results are compared with various the-ories of grain boundary migration and with observations made prev.iorlsly of grain boundary migration in similar specimens of zone-refined lead containing tin additions. A previous investigation by the authors dealt with [he temperature dependence of grain boundary migration in bicrystals of zone-refined lead containing small additions of tin.' It was shown that tin additions as low as a few parts per million cause a large decrease in the grain boundary migration rate at any given temperature, as well as a marked increase in the temperature dependence of the migration rate. It was found that existing theories of grain boundary migration. based on the motion of dislocations. or upon the concept of atom transfer in groups across the boundary (group process theory). or upon the control of grain boundary motion by volume diffusion of impurity atonls along with the boundary. are incapable of accounting for the observations. The single process theory of grain boundary migration. which is an absolute reaction rate calculation based on the transfer ui atoms singly across the moving boundary, was found to predict the migration rate reasonably well for a number of boundaries whose motion was shown to be very little influenced by impurities, but not for boundaries whose illation was influenced markedly by impurities. It was concluded that the elementary process of grain boundary migration involves the activation of single atoms during transfer across the boundary. and that inadequate knowledge is available to permit the influence of impurities to be properly taken into account. The present study was initiated to check the validity of the above conclusions with other alloy systems, namely high-purity lead with small additions of silver and of gold. Both silver and gold diffuse faster. and with a lower activation energy of volume diffusion. than does tin in lead;' consequently, a study of the effects of silver and gold on grain boundary migration in high-purity lead offered a means of testing theories of boundary migration based on bulk diffusion of the solute (eg. ref. 3). In addition. it was hoped that the present work, in comparison with the results for tin in lead, would provide information concerning which factors are important in determin- ing the interaction between solute atoms and a grain boundary. EXPERIMENTAL PROCEDURE The preparation of bicrystals of zone-refined lead, with various silver or gold additions, was identical to that previously described for the lead-tin alloys.''4 Each bicrystal consisted of a striated crystal which was grown from the melt. and an adjacent striation-free crystal which was introduced by artificial nucleation and growth.''4 The striation or lineage substructure in the melt-grown crystal provided the driving force for grain boundary migration. During the preparation of striated single crystals by growth from the melt, it was found that silver or gold concentrations as low as 2 or 3 ppm by atoms were sufficient to cause formation of the hexagonal cell structure. which is due to the presence of impurity, during freezing. This structure is revealed on the solid-liquid interface by decanting the liquid during freezing. The hexagonal cell structure was observed previously4 in zone-refined lead crystals with tin contents above approximately 200 ppm by atoms. These concentrations of silver, gold, or tin are in agreement with the predicted amounts required for cell formation in lead,5'6 under the present conditions of freezing.4 The absence of cell structure at decanted interfaces, therefore, served as a useful indication that the silver or gold contents were less than 2 or 3 ppm by atoms in the specimens as grown. It was found that grain boundary migration occurred only very slowly when the solute content approached that necessary for cell formation. As a result, the present experiments were conducted with silver or gold additions less than 1 ppm by atoms. This impurity level is well within the solid solubility limits for silver and gold in lead.7 The annealing treatments, measurements of grain boundary velocities, and orientation determinations were carried out as described previously.' However. each bicrystal was also chemically polished in a solution consisting of 8 parts glacial acetic acid and 2

Jan 1, 1961