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By H. J. Hand

Statistical methods are becoming increasingly important for interpreting routine reports, or for analyzing special test data in industrial plants, such as steel plants. They have already become practically a necessity to the plant metallurgist. A paper by Chancellor, 1 written in 1933, gives many examples of the benefits the plant metallurgist can derive from the use of these methods. The present paper discusses applications of importance to many others who must analyze reports in the steel plant, as well as other examples of interest to metallurgists. Statistical Methods Logically Suited to Plant Problems.—Statistical methods are not new as a branch of mathematics. Until comparatively recently, however, practical applications were confined mainly to actuarial science, biology, and economics; fields in which an observed result is obviously influenced (and often determined) by a complicated set of variables more or less constantly tending to affect it. As pointed out by Daeves,2 a decade or more ago, problems in industry are basically similar to those in these other fields in that a given result is at least partly due to that chance combination of causes happening to be present at the time. When trying to do the same thing repeatedly, constant results are never attained; they vary about the desired result with more or less well defined mathematical regularity. Such a condition arises out of the great number of factors tending to affect the final result. If statistical methods are so valuable to the biologist or economist, why then should they not also be of great value to plant managers and engineers, and to all who must interpret reports from various sources in the industrial plant? Within the last few years, industry has become conscious of this situation, and the use of these methods has been rapidly expanding in such p1ants. Many Useful Statistical Devices Available.—Many statistical methods of attack are available for the analysis of plant data. It is the object of

Jan 1, 1938

By H. J. Hand

Statistical methods are becoming increasingly important for interpreting routine reports, or for analyzing special test data in industrial plants, such as steel plants. They have already become practically a necessity to the plant metallurgist. A paper by Chancellor, 1 written in 1933, gives many examples of the benefits the plant metallurgist can derive from the use of these methods. The present paper discusses applications of importance to many others who must analyze reports in the steel plant, as well as other examples of interest to metallurgists. Statistical Methods Logically Suited to Plant Problems.—Statistical methods are not new as a branch of mathematics. Until comparatively recently, however, practical applications were confined mainly to actuarial science, biology, and economics; fields in which an observed result is obviously influenced (and often determined) by a complicated set of variables more or less constantly tending to affect it. As pointed out by Daeves,2 a decade or more ago, problems in industry are basically similar to those in these other fields in that a given result is at least partly due to that chance combination of causes happening to be present at the time. When trying to do the same thing repeatedly, constant results are never attained; they vary about the desired result with more or less well defined mathematical regularity. Such a condition arises out of the great number of factors tending to affect the final result. If statistical methods are so valuable to the biologist or economist, why then should they not also be of great value to plant managers and engineers, and to all who must interpret reports from various sources in the industrial plant? Within the last few years, industry has become conscious of this situation, and the use of these methods has been rapidly expanding in such p1ants. Many Useful Statistical Devices Available.—Many statistical methods of attack are available for the analysis of plant data. It is the object of

Jan 1, 1938

By W. M. Rust, W. D. Mounce

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimenlally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so universally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretatioils of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in. in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resist-

Jan 1, 1946

By W. M. Rust, W. D. Mounce

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimenlally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so universally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretatioils of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in. in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resist-

Jan 1, 1946

The Section on Aerial Geologizing of the American Institute of Mining and Metallurgical Engineers convened on Monday afternoon, Feb. 17, 1936, during the Annual Meeting of the Institute. Mr. Theodore Marvin presided. Chairman Marvin.—We hope to get through with the papers on the program in time so that you can examine the instruments that are displayed here, and also the photographs and air views brought by the Fairchild people. This is what we might call the first bread and butter session of the Aviation Committee. The group, as many of you know, was started at the request of the Board of Directors two years ago. We have had two sessions since then, both of them of a somewhat general nature, their purpose being to point out the reasons why mining and petroleum engineers should be more interested in the facilities of aviation. Today we have two papers. The first is one by Mr. Eliel, of the Fairchild Company's California branch. In Mr. Eliel's absence, Mr. Gale, of the Fairchild Company, will read it. C. H. Gale.—Before I begin to read Mr. Eliel's paper, I would like to point out two instruments that he mentions- One is what he calls the solar-navigator, a new type of aerial navigating device which he has developed for use in flying cameras in aerial surveys. Flying a camera at high altitudes over unfamiliar territory is a very difficult procedure and only a few pilots in this country can do it. So far as I know, this is the first time this device has been discussed in public. Another facility I want to refer to in advance is the use of the stereoplanigraph in making contour maps from photographs. This is an extremely interesting procedure, which we are appreciating more than ever at the present time.

Jan 1, 1937

By Wayne Phillips, Anatalia Silva, Robert Henderson, Tondo. Luis

"Kinross’ Paracatu Mine has 20 years of operational success as one of the lowest grade milloperated gold mines in the world. At year end 2005, Paracatu’s Proven and Probable Reserves were 1.18 billion tonnes at a grade of 0.40 g/t Au, containing a total of 15.2 million ounces of gold.In 2005, the plant processed 17 Mt of ore and produced 180,519 ounces of gold at a cash cost of US$274/oz. An investment of US$470 million has been approved to expand production to 61 Mtpa in 2009 which will extend mine life to 2036. During the period from 2009 to 2013 the project is expected to produce an average annual output of approximately 557,000 ounces of gold at an average cost of sales of approximately $230 per ounce.The soft, friable ore containing readily leachable gold associated with sulphides lends itself to simple processing. The process flowsheet consists of crushing, grinding, gravity recovery, flotation, concentrate leach and carbon adsorption to produce bullion bars. This paper describes the current operation, the deposit’s unique metallurgical features and the future expansion plant that has been designed to optimise recovery of gold.INTRODUCTIONRio Paracatu Mineração (RPM), a wholly owned subsidiary of Kinross Gold Corporation, operates the Paracatu mine. The mine is located in Brazil, 230 km south west of Brasilia in the north west portion of the State of Minas Gerais. The city of Paracatu, which has a population of 83,000 people, is just 2 km south of the mine."

Jan 1, 2007

By K. Severin, B. Flanigan, P. Marion

“Plutonic-related” gold deposits in Interior and SW Alaska (Tintina Gold Belt) vary significantly in size, grade, vein/deposit morphology, depth of emplacement, distance from causative pluton and metal association. Metal associations such as Au-Bi and Au-As-(Sb-Hg) are a good empirical indicator of depth of emplacement and distance from causative pluton and have been used successfully in exploration. Results from a variety of analytical techniques also suggest a phenomenological cause for these metal associations, e.g. gold and bismuth have linked metallogenesis at high temperatures and thus are best correlated at deposits that are deep and/or close to causative intrusions.

Jan 1, 2000

By J Parnell, B Manson

Bitumen occurs in the basins in reservoir sandstones, in veinlets close to hydrocarbon source rocks, in veins through lava beds and in sulphide-mineralised veins where it is closely associated with, but predates, the sulphides. The role of organic matter was probably in enhancing metal reduction by creating a low-Eh environment rather than in metal transport. Coeval euhedral quartz crystals or albite in sulphide-bearing carbonate veins provide evidence of an aqueous component to the hydrocarbon fluid

Aug 1, 1995

By D Craw

The Rise and Shine Shear Zone is a mineralised low angle deformation zone traceable for at least 7 km through biotite zone schist of the Dunstan Range, central Otago. Rocks from the shear zone obtained from recent drillholes are unweathered and facilitate paragenetic studies. There is a progression of mineral deposition from semiductile foliation-parallel shearing, to subsequent folding, and brittle fracturing. Sheared rocks are dominated by microshears containing fine grained hydrothermal muscovite and rutile that has recrystallised from metamorphic muscovite and titanite respectively. Euhedral pyrite occurs within segregations in the schist and is locally brecciated by the shears.   Arsenopyrite occurs within microshears and is intergrown with hyrothermal muscovite. Fractures within relatively undeformed schist are filled with ankerite, siderite, chalcopyrite, sphalerite and galena and these veinlets also crosscut the microshears. Locally the schist is folded and zones of brecciation, silicification and vein deposition overprint the rock. Vein quartz and albite predominate and arsenopyrite and gold infill breccia matrix and crosscutting veinlets. Sulphide deposition began in the later stages of metamorphism with pyrite deposited in quartz-albite segregations. Subsequent shearing caused brecciation of some grains and accompanied deposition of arsenopyrite ¦ gold and rare sulphides along foliation-parallel microshears. Minor amounts of chalcopyrite, sphalerite and galena were then remobilised in ankerite veins that crosscut the shears. In areas of high strain, arsenopyrite was then deposited as euhedral grains in veins and breccias. Synmineralisation deformation caused the brecciation of some grains and gold was deposited infilling fractures in the arsenopyrite. The paragenetic sequence shows gold mineralisation occurred in two distinct sets of structures (semiductile and brittle) that formed at different times in the formation of the shear zone.

Jan 1, 2006

By Dominique Francois-Bongarcon

The rational and optimal determination of the design of a mining exploitation is a very intricate and difficult problem : the parameters are numerous, some technical, some economic or technico-economic which cannot be fully controlled; beside, deposits are estimated from very limited information and the choice criteria are not always quantitative, the economic context has to be anticipated by several years, and even the technological limits can change tomorrow. So, although very clever and performing numerical algorithms have been developed in recent years for open-pit design, we consider that this problem has not really been solved satisfactorily until now. The reasons are that people have concentrated their efforts on informatical algorithmical problems, and have assumed that the technical and economical data are well defined at the time of the study, which is generally not true. In particular, the mere fact of assigning dollar- values to blocks in order to maximize the total cash-flow is generally unrealistic because of the uncertainty of the data used. Consequently, the significance of the unique pit obtained as a result of these algorithms is questionable.

Jan 1, 1981

By Wolfgang Gütter

India is targeting to boost its electrical capacity from 100 GW to 200 GW within the next 10 years. The National Hydroelectric Power Corporation (NHPC) has decided in2001 to take execution of the 800 MW Stage-II of the prestigious 2,051 MW Parbatihydrol electric project in Kulu district of the northern province Himachal Pradesh. Two parallel 30° inclined underground pressure shafts of 1.542m in length each will be excavated in different geological formations and lined with hexagonal concrete segments by a hard rock double shield TBM. That kind of heading will be a novelty to India and an innovative method for inclined pressure shafts. The 4.88m Mitsubishi DSTBM will be assembled underground on a swivelling steel platform especially designed for the launching as well as for the acceptance of the TBM in the upper cavern of each shaft. The hexagonal segmental lining system causes a significant higher job safety than an open TBM with conventional support. Each ring consists of four honeycomb segments with 20 cm thickness. After finalisation of the excavation a steel liner will be installed and concreted. The Joint Venture Jäger-Seli will perform the two pressure shafts as a sub-contractor for the Indian company Gammon India Ltd.

Jan 1, 2005

By M Kozikowski

The primary purpose of these investigations is to determine dewatering requirements and likely impacts associated with mining operations. Standard aquifer testing techniques were carried out at multiple locations within the Ord Range near Pardoo, Western Australia. Aquifer properties of an oxidised haematite orebody were calculated from test pumping data conducted in five fully penetrating test bores. Hydraulic properties of the Ridley magnetite orebody were calculated based on short term constant rate pumping tests, and packer tests. Packer tests were conducted in undeveloped and uncased exploration holes and diamond core holes. The new data sheds light on the hydrogeological properties of this previously unexplored region of Western Australia.Aquifer testing procedures for each bore included a preliminary step test followed by a constant rate test. Recovery data were collected in each bore over a period of four to six hours. Prior to testing, background water levels and water samples were collected in a network of monitoring and exploration bores to establish baseline water levels, gradients and water quality. Water quality within the bedrock of the Ord Range varies from 2000 to 5500 mg/L TDS whereas water quality within the alluvial sequence of the De Grey River is highly variable (400 to 2500 mg/L TDS), but is predominantly brackish with some water of potable quality which is used to supply Port Hedland. Test pumping supports the conceptual hydrogeological model that consists of a pod like orebody (aquifer) surrounded by low permeability waste rock (BIF), with very weak hydraulic connection to the adjacent alluvial systems. Calculated hydraulic conductivity from test pumping data across Pardoo ranged from 0.01 to 59 m/d, depending on deposit tested.A groundwater model was used to simulate dewatering required in proposed pits and to estimate the impact of dewatering on the surrounding shallow alluvial aquifers. Test pumping and numerical groundwater flow modelling indicate the proposed below water table pits can be successfully dewatered utilising in pit dewatering production bores. Yields from individual dewatering bores will reduce with time due to the reduction in saturated aquifer thickness.Based on the numerical groundwater modelling and field investigations the likely impacts to the adjacent De Grey River alluvial aquifer system (within the Priority 1 De Grey River Water Reserve) resulting from mining and dewatering activities is considered minimal. Recalibration of the groundwater model will be undertaken once several months of dewatering data are available.The aim of this paper is to present a range of aquifer parameters derived through standard aquifer testing techniques for an area previously unexplored in terms of hydrogeological characteristics. It is the goal of the authors to provide this comparison data set for future work in similar geologic media.

Jan 1, 2009

The purpose of this paper is to describe briefly the clean-up procedure adopted at the treatment plant of Paringa Mining & Exploration Co. Ltd. at Kalgoorlie, Western Australia.A clean-up is carried out at the end of each four-weekly period, and all figures subsequently quoted are taken from a summary of the results of the eight periods ending 8th April, 1941.STRAKING AND AMALGAMATIONOf the total gold won 22· 77 per cent. is recovered by straking and amalgamation.The discharges of both the primary and secondary ball mills are pumped over a common set of five ten feet long by three feet wide straking tables, set at an angle of 10 degrees, before passing to the 14 ft. diameter by 30 ft. by 8 ft. Dorr bowl classifier.This classifier is in closed circuit with both of the ball mills, hence the whole of the circulating load of the fine grinding circuit, which approximates to 800 per cent., is required to pass over the straking tables. For convenience in handling, corduroy cloths are used in lengths of 5 feet, and are picked up and replaced by clean cloths at four-hourly intervals. The avaHable straking area provided is, therefore, 900 square feet, or approximately 3·30 square feet per original ton per 24 hours. The density of the pulp passing over the tables is about 54 per cent. solids, the area provided per ton of pulp per 24 hours being approximately o· 2() square feet. Washing of the corduroy cloths is carried out on the day shift only, about 800 lb. of strake concentrate being obtained daily.This concentrate is sluiced from the washing trough on the elevated straking floor to the 4 ft. by 2 ft. diameter amalgamating barrel located in the gold room below.The barrel is of standard design and is rotated at 25 r.p.m. It is charged each day at 4 p.m., and grinding of the strake concentrate at approximately 70 per cent. solids is continued until 8 a.m. the following day. The barrel is then stopped, and the contents generously diluted with water, and after a few minutes rotation some of the slime is carefully poured off through the small discharge hole. This dilution and decantation is repeated until a good deal of the valueless slime has been removed.A further quantity of strake concentrate is then charged to the barrel, which is allowed a further 16 hours grinding period. After again diluting and decanting, approximately 25 lb. of mercury and 15 lb. of lime are added to the charge, which is then given an amalgamation period of 2 hours before cleaning up.By the process of grinding, diluting and removal of slime by decanting...

Jan 1, 1941

By Frank A. Aplan, Barbara J. Arnold

INTRODUCTION Coal flotation is a fine cleaning process usually present in all but the older preparation plants. It is typically used to clean either the -28 mesh (-500 pm) or - 100 mesh (- 150 pm) raw coal fines, and it is the only commonly used preparation method that can effectively recover coal particles finer than, say, -200 mesh (74 pm). To place coal flotation into its proper context, it should be noted that the bulk of the raw coal sent to preparation plants is treated by gravity concentration. On a worldwide basis, from 0 to 40% of the raw feed to a preparation plant is treated by flotation, while in the US only about 10% of the raw coal feed is floated. Roughly, 50% of US preparation plants use flotation to process at least a portion of the raw coal feed, although most of the newer plants incorporate flotation into their flowsheet. Historically, the process has only been used to treat the raw coal fines naturally occurring after mining and a minimal amount of crushing at the preparation plant. This is in sharp contrast to ore flotation where, typically, the entire tonnage is first ground and then floated. As a consequence, of the approximately 500 Mt of raw coal treated by preparation in the US yearly, it is estimated that only about 40 Mt are sent to the flotation circuits (producing -30 Mt of clean product).'O1 This small tonnage compares with about 400 Mt of ores treated annually in the US by flotation. By analogy to ore flotation, where it is an effective, large tonnage, low cost, easy to operate process, its potential in coal preparation should be great. Reasons why it has not achieved a greater potential in coal preparation have been attributed by Aplan 102 to: 1. Indifferent results in removing sulfur and ash. 2. Difficulty in floating low rank and oxidized coals. 3. Inability to make clean separations with the finer sizes. 4.Inability to clean slurries with a high percentage of clay. 5. Problems with water chemistry. 6. Competition with effective, gravity coarse-cleaning methods. 7. Low value of coal historically. 8. Dewatering problems. 9. Transportation and storage problems with coal fines. 10. Marketing problems with coal fines. 11. Inadequate attention to the process in the plant. 12. Inefficient use of capital and operating monies. Inadequate attention to procedures, machines, and processes.

Jan 1, 1991

Jan 1, 1970

By M. J. Pool, with Appendix by Larry Kaufman, R. W. Krenzer

Thermodynmic properties of the Cu-Mn system have been deterrrzined in the temperature range 973" to 1273°K by measuring the vapor pressure of manganese in equilibrium with alloys of compositions varying from 0.13 to 0.91 rnole fraction manganese using the Knudsen effusion technique. Activities of manganese calculated from the measured vapor pressures show large positive deviations. Calculated heats and entropies of mixing are positive with a maximum occurring at approximately 0. 7 mole fraction manganese. ThE investigation of thermodynamic properties of binary systems involving transition metals is of considerable interest at the present time. The incomplete subvalency electron levels of transition metals lead to unusual behavior in some alloys, and considerable information can be obtained by determining the thermodynamic characteristics of these systems and relating the thermodynamic behavior to observed physical properties. The Cu-Mn system, shown in Fig. 1,' provides an example of an alloy system in which the determination of the equilibrium phase diagram and various physical properties has received considerable attention, but very little work has been done on measurement of the thermodynamic properties. Elemental copper and manganese have comparable electronegatives, atomic sizes, and cohesive energies, but differ in crystal structure. They form a continuous series of solid solutions only at high temperatures and the structure varies in a continuous manner from fcc at the copper-rich end to fct at the manganese-rich end.' The purpose of this investigation was to measure the vapor pressure of manganese over a series of Cu-Mn alloys and from these values determine the thermodynamic properties of the binary system. Vapor pressure measurements were made in the temperature range 973" to 1273"K, remaining within the solid-solution region for each alloy studied. EXPERIMENTAL PROCEDURE The relative thermodynamic properties of solid Cu-Mn alloys were determined from vapor pressure measurements by means of the Knudsen effusion tech- nique. Several discussions of the theory can be found in the literature. In the case of copper and manganese, it is assumed that manganese is the only component subliming, so the vapor pressure of manganese over the various alloys can be determined directly by measuring the weight loss of the effusion cell. This is a valid assumption since the vapor pressure of manganese is about four orders of magnitude higher than the vapor pressure of copper in the temperature region of interest. The vapor pressure of manganese over the alloys at any given temperature is then related to the weight loss of the effusion cell per unit area per unit time. An upper limit of 1.5 x 10"s has been measured for the ratio of polyatomic to monoatomic molecules for manganese vapor in equilibrium with solid manganese at 1180°K, so it was assumed that manganese vapor is monoatomic. The effusion cells, fabricated from high-purity alumina, are 26 mm high, 18 mm OD, and have a wall thickness of 1 mm. Three different sized holes of 2.03, 2.54, and 3.18 mm diam were drilled in the lids from the inside face to minimize chipping, and the lids were then slip-cast onto the cells to provide a gas-tight seal. Alumina was selected for this particular application both because of its resistance to thermal shock and reaction with manganese vapor. In the ideal case, the orifice of the effusion cell should have a knife edge so that effusion through the orifice

Jan 1, 1970

By F. Haessner, M. Wilkens, U. Jakubowski

ThOUGH at present there is a wide range of possibilities for the quantitative determination of preferred orientations, pole figures of identical specimen material have not been determined by different methods as yet.''' In this paper a comparison of (Ill), (200), and (220) pole figures is presented which were obtained from a 95 pct cold-rolled high-purity cop- per sheet (99.9998 pct Cu), by three different methods. The three methods are: a) The combined X-ray reflection-transmission technique of plane samples by schulz3 and Decker, Asp, and Harker. 4 A Siemens texture goniometer was used. The experimental details are described elsewhere. 6 b) The X-ray reflection technique of spherical samples by Jetter and Boric.' A Siemens texture goniometer with some modifications was used. The samples were prepared by sticking 140 polished sheets together with an adhesive and machining a sphere (20 mm diam).* Additional

Jan 1, 1967

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By R. G. Vardiman, M. R. Achter

Observations of dislocation structure in niobium are presented using two techniques. Triangular pits developed by electroetching are confined to orientations in the stereographic triangle between the (111) pole and planes of the (1ll) zone and require the presence of carbon. Some unusual electroetching phenomena at other orientations are noted. A chemical etch of dislocations decorated by the addition of carbon to 50 ppm reveals the complete dislocation line structure in a surface layer up to 30 p deep, with a resolution of less than 1 p. This effect is independent of surface orientation. The structure of subboundary nets may be resolved for misorientations up to about 1'. Dislocation structures found in strain anneal grown crystals, such as helices, prismatic loops, and high-density areas, are observed. The measurement of dislocation density is discussed and values obtained in different ways are compared. IN the course of some work on the response of refractory metals to thermal-mechanical treatments, it was desired to examine the defect structure of relatively low dislocation density crystals of niobium in bulk form. Surface and bulk methods for the observation of dislocations have been reviewed by ~melinckx,' and include etch pitting, decoration, and various X-ray techniques. The dislocation line structure has been developed by decoration in a few metals, although observations were limited to certain orientations, or by the coarseness and nonselectivity of the precipitate. The most commonly used technique is etch pitting. In niobium, etch pits have been developed chemically'0," in material of high impurity content and electrolyti-cally'' in relatively pure material. In this paper, etch pits developed electrolytically, and the dislocation line structure of a surface layer developed by decoration and chemical etching, are examined, and observations are presented from both techniques. EXPERIMENTAL METHODS Our starting material was electron-beam-melted niobium, swaged to 4 or -in.-diam rod. Chemical analysis is given in Table I. Single crystals were grown by a strain anneal technique using 1 to 2.5 pct of strain and growth temperatures of 1700" to 2300"~.'~ Some crystals grown by zone melting were also examined. The desired surface orientation was exposed either by spark machining or by sectioning with a cut-off wheel and prepared for etching by electro-polishing.

Jan 1, 1969

By Amitava Gangulee, Michael B. Bever

The effects of changes in short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions have been investigated. The heats of formation at 273°K of several alloys after two different thermal treatments were measured by liquid metal solution calorimetry. Their electrical resistivities were measured at temperatures ranging from 4° to 773°k. Tensile tests and microhard-ness measurements were carried out at room temperature. An effective short-range order parameter and an effective interaction energy are defined. The measured changes in the properties are interpreted in terms of these quantities. The short-range order parameter is evaluated separately from calorimetric and X-ray data; the results are in fair agreement. Increasing short-range order lowers the resistivity of- the silver-rich Ag-Mg alloys but does not measurably affect the temperature dependence of the resistivity. Short-range order increases the yield stress of these alloys but does not affect the ultimate tensile stress. Changes in the effective short-range order parameter independently obtained from measured changes in the heat of formation, resistivity, and yield stress are in fair agreement. THE thermodynamic, electrical, and mechanical properties of solid solutions have been investigated as functions of composition in many alloy systems, but the effects of configurational variables, such as short-range or long-range order, on these properties have received much less attention. The silver-rich terminal solid solutions in the system Ag-Mg are well-suited for the investigation of the effects of order. The composition of these solid solutions may be varied over a range extending to about 27 at. pct Mg.1 Appreciable short-range ordering is likely to take place in these solid solutions; the degree of short-range order can be varied by suitable thermal treatments. In the alloy Ag3Mg long-range ordering is possible.2 This paper is primarily concerned with the effects of short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions.-The long-range ordering transition is the subject of a concurrent paper.3 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Ag-Mg alloys containing up to 26.4 at. pct Mg were prepared by melting 99.99 pct pure Ag (obtained from Baker Chemical Co.) and 99.99 pct pure Mg (obtained from Eastman Chemi- cal Co. or Johnson Mathey & Co.) in graphite crucibles under molten potassium chloride. The solidified ingots were homogenized at 823°K for 10 days in evacuated Vycor capsules. A surface layer 6 in. thick was then removed by machining. The ingots were swaged into rods (2.5 mm diam) which were drawn into wires (1.0 mm diam). The wire specimens were annealed at 773°K for 24 hr in vacuum and either quenched into iced brine or cooled to room temperature over a period of 15 days. The average grain diameter (obtained from the linear intercepts) was about 0.1 mm. 1.2) Calorimetry. The heats of formation of the alloys were measured in a tin solution calorimeter as the difference in the heat effects of alternate additions of samples of an alloy and the mechanical mixture of its component elements. The additions were made from 273°K to the bath at about 623°K. The heat effect on addition of the alloys was approximately 5.5 kcal per g-atom. The procedure and the method of calculation have been described.4 1.3) X-Ray Diffraction. Short-range order parameters of two alloys were calculated from diffuse scattering intensities,' obtained with briquettes made from powdered specimens. A GE-XRD 5 diffractometer with filtered copper radiation was used. The absolute intensities were based on calibrations with paraffin. 1.4) Resistivity Measurements. The electrical resistivities were measured by a potentiometric method in which the potential drop across the specimen was compared with that across a standard resistance. For measurements below room temperature, the specimens were immersed in liquid helium (4°K), liquid nitrogen (78°K), dry ice and trichloroethylene (195°K), or ice and water (273°K). Measurements above room temperature were made on specimens held in a furnace under helium or in vacuum. The resistivity measurements were reproducible to ±0.5 pct or less. 1.5) Mechanical Tests. Tensile tests were carried out at room temperature with a Tinius-Olsen XY elec-tromatic Universal testing machine. Wire specimens (nominal gage length 1 in.) were used. The strain was measured with an extensometer, which had a sensitivity of 4 x 10-5; the strain rate was 10-3 min-1. Microhard-ness measurements were made with a square-pyramid indenter and a 100-g load.11 2) RESULTS AND DISCUSSION All measurements were made on two parallel sets of specimens, one quenched and the other slowly cooled from 773°K. The reported values are the averages of at least three measurements. In the range of magnesium concentration substantially below that of the composition Ag3Mg, quenched alloys have less short-range order than slowly cooled alloys. As the magnesium concentration approaches that of Ag3Mg, slow cooling develops long-range order. Quenching sup-

Jan 1, 1969