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By James D. Reilly

13.1-1. Introduction. COAL RESERVES OF THE UNITED STATES. Bituminous coal is the most abundant fossil fuel in America. With reserves of 1,660 billion tons and assumed recovery of 5070, there is more than 830 billion tons of recoverable coal--enough to assure ample supplies of energy for centuries. Looking at Fig. 13.1-1, coal is found in a majority of the states, including [ ]

Jan 1, 1968

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By D. L. Albright, R. W. Kraft

A technique is described whereby the study of crystal perfection through the use of conventional X-ray rockite curves is extended to three dimerzsions. Specinzens of unidirectionally solidified eutec-tic alloy which consist of a nearly perfect parallel arrangement of alternating Platelets of Al and CuAl2, but which contain lamellar faults have been analyzed by this technique in conjunction with X-ray microscopy. Analysis of the data has shown that some rotational symmetry about the growth direction occurs, that small groups of lamellae between faults diffract as a unit, and that the misorientation caused by a fault is on the order of a degree of arc. A eutectic-grain can be defined as that portion of a eutectic specimen in which the crystallographic orientation of each phase AND the microscopic or met-allographic orientation of the phase particles have fixed angular relationships one to another. Eutectic-grains of the A1-CuA12 eutectic, which is a normal lamellar eutectic, have been grown by unidirectional solidification and identified as such.1-3 To a first approximation, a eutectic-grain in this system consists of two interpenetrating single crystals which are related to each other and to the lamellae themselves as follows:

Jan 1, 1962

By T. V. Falkie, Robert Stefanko

Much criticism has been directed at the Coal Mine Health and Safety Act of 1969 from many sources, but few specific charges have been leveled, at least publicly. Yet, if the criticism is truly valid and can ever hope to become constructive, the issues must be approached head on. Therefore, the authors consider this an initial article and invite responses from others for contributions in subsequent issues. Dialogue is today's popular term and perhaps many of the problems associated with the implementation of the Act are the lack of communication between interested parties. There are two criticisms generally made concerning the philosophical approaches taken in the Act. The first is that there is an over-kill in some of the legislation, some provisions are not justified based on past accident history and economic considerations. Generally speaking in this category, no order of priority was considered consistent with safety and economy. The second category includes those situations where new provisions were imposed to improve safety in one area without adequately considering the consequences in another area, let alone the economics of the situation. While the authors do not always agree with the placement of items in these two categories by some industrial representatives, they will give specific examples that they believe may have a certain degree of validity.

Jan 1, 1971

By H. F. Silliman, Daniel R. Hull, John R. Freeman

IN the normal operation of a brass-rolling mill, sheet and strip has, for the most part, been finished in comparatively thin gauges, involving a substantial amount of coldwork and a considerable number of anneals. This condition has been disturbed by the prep0nderance of cartridge brass, which is not rolled to thin gauges, and particularly by brass for artillery cartridge cases, on which the mill may finish its work at a thickness between 0.400 and 0.900 in. Obviously, the amount of rolling and the number of anneals to which such a product can be subjected are small compared with strip that is carried to a thickness of a few hundredths of an inch. As a result, critical examination into the internal condition of metal has been made on an extensive scale at a stage of manufacture that would not, in normal times, have been chosen for complete inspection. Under these conditions, a type of defect has been recognized that is not seen at thinner gauges. It might be more accurate to call it the appearance of a defect, since it refers to an apparently laminated, discontinuous structure, which, in fact, does not exist as such, and disappears after suitable treatment. For this reason it has been called a phantom lamination, which the authors consider an appropriate term. It is the purpose of this paper to describe the phenomenon and the conditions of its occurrence and, at least tentatively, to discuss its nature and cause. Great numbers of phantoms may be found in 2: 1 brass, either hot-rolled or cold-rolled. They are also found in 70-30 brass, sometimes when hot-rolled and generally when cold-rolled. It is not believed that phantoms are confined to these alloys but this paper is limited to them for the purpose of description. HOT-ROLLED 2:I BRASS For illustration, therefore, a typical cake of hot-rolled 2: 1 brass has been chosen. This was rolled to a slab 7/8 in. thick, from a casting 5 in. thick by 24 in. wide by 18 in. high, which was believed to have been sound. After hot-rolling and cooling, the slab was sheared and a portion of such a shear cut is shown in Fig. 1. It would be difficult to convince anyone viewing this specimen that the metal was not unsound. The impression would be confirmed by the appearance of a tensile break, as shown in Fig. 2. This is an ordinary tensile-test piece from metal just described. Although there was nothing in its tensile strength or elongation that suggested unsoundness, it appeared run through with pipes and laminations. To question the reality of such a condition would imply questioning the obvious. But, considering the history of the metal, it w0uld be difficult to believe that it could be so bad as it appeared. It seemed reasonable, though, that if the defects were what they appeared to be, they could be traced back from the sheared or broken face.

Jan 1, 1945

By C. W. Waidner

THE standard scale of temperature that it is attempted to realize in practice is the centigrade thermodynamic scale, as defined by Kelvin about the middle of the last century. This scale would be exactly realized with a perfect1 gas in an ideal gas thermometer, and is closely realized with the more permanent gases. From the departure of certain properties of these gases from those of a perfect gas, it is possible to deduce the amount of the departure of the temperature scales, defined by their use, from the thermodynamic scale. In nearly all the precise experimental work done during the latter part of the last century, it was necessary for the experimenter to establish his own gas-thermometer scale, and the labor involved in this was often greater than that involved in the prime object of the experimental work undertaken. The experimental difficulties involved in gas thermometry led to the establishment of temperature scales differing from one another by amounts considerably greater than could be accounted for by the differences in the properties of the gases used. Results were, therefore, expressed in terms of somewhat different temperature scales, snaking correlation of such results difficult and uncertain.

Jan 9, 1919

By H. Scott

SINCE Böhler discovered, in 1903, on cooling certain alloy steels, the phenomenon of a new and lower temperature transformation than the usual Ar3_2_1 obtained by increasing the maximum temperature to which the material was heated, much has been published' connecting this phenomenon with a large number of dissimilar steels of high alloy content. From the fact that the transformation divides itself, taking place at two widely separated temperatures, it has been called a "split transformation." The, significant facts established by recent investigators' are: that when the' transformation occurs at the higher temperature Ar', troostite or a decomposition product is formed, and that when the transformation occurs at the lower temperature Ar", the resulting structure is martensite. The terminology Ar' and Ar" adopted here is that of Portevin.3

Jan 2, 1919

By Alfonso W. Ovalle, Héctor R. Albornoz

INTRODUCTION The El Teniente Mine of Codelco-Chi le has extracted 588 mil lion tons of ore in its 77 year history for a total copper output of 8.800.000 tons. The mine production has been obtained mainly by traditional block-caving where grizzlemen using a hand held lever send ore through long-raises to load trains. At present the mine is about to introduce mechanized block-caving using LHD equipment to extract the primary rock. This paper describes this method which will be tested starting next month by caving an 11.000 square meter block. THE PRIMARY ROCK PROBLEM The secondary enrichment sulfides of the El Teniente ore body have characteristics which makes a standard unmechanized block-caving practice very successful. In the 60's parts of blocks encountered primary ow in the Teniente 1 and Sub-13 levels which proved to be extremely hard to extract. These foretold the obstacles that arised in the central part of the Teniente 4 level. Preparation of a completely primary 8.100 square meter block started in 1970. Its undercutting was completed by the end of 1972 and by 1973 the problem of mining the primary rock was clearly visualized. The numbers below describe the difficulties in mining this block: -Long-hole drilling rate is 90 m (270 ft) per shift in secondary rock and 37 m (110 ft) in primary. - Undercutting which is completed in 9 shifts in secondary took 180 shifts in the primary block. - Average grizzlymen productivity in secondary is 250 tons per shift while in primary it is only 25-30 tons, both at 343 mm (13 1/2 in. ) grizzly opening. - Powder consumption for secondary blasting increased from 8 grams per ton in secondary to 84 in primary. - The protection pillar between the under- cutting and the production levels was 60% broken in primary while 20% is usual for secondary. - Extraction advanced 5 cm per day in primary while a 50 cm per day rate is the aver- age in secondary. This is the main reason that after 8 years this primary block has a 20% extraction. Secondary blocks take 1.5 to 3 years to complete their extraction. - 80% of the boulders in primary rock are larger than 343 m (13 1/2 in.) with 10-20 % of them larger than 3 meters. -Direct cost of production (preparation, undercutting, extraction and haulage), using the traditional block-caving design for secondary rock, increased 3.5 to 4 times when used in primary rock. The following indicators of Table 1 show the rock characteristics differences.

Jan 1, 1981

By L. G. Jones

An approximate method of calculation is developed in this paper which allows duplication of radial unsteady-state gas flow computer results where Darcy's law applies, such as those reported by Aronofsky and Jenkins and Bruce, Peaceman, Rachford, and Rice. Moreover, the new calculation method can be used to obtain results for radial unsteady-state gas flow obeying the quadratic flow law proposed by Duwez and Green. Means are discussed for predicting well behavior at single or superimposed flow rates in finite or infinite reservoirs, determining reservoir rock properties from well-test data, reproducing and interpreting back-pressure test data, and determining the radial extent and reserves of gas reservoirs from well-test data. Example calculations are presented for gas flow following both Darcy's law and the quadratic flow law. INTRODUCTION Since the publishing of U. S. Bureau of Mines Monograph 7,1 most gas-well testing methods have been based on the equation q = y (pl2 - pw2)a, where q = production rate, pl and pw, are formation pressure and sandface pressure, respectively, and y and a are constants to be obtained from test data. These methods, used for predicting both deliverability and "open-flow" capacity of gas wells, have been useful and accurate in many cases but unsatisfactory in others. Even at best, however, they do not supply information about the formation or lead to an understanding of nonsteady-state gas flow in porous media. Many theoretically based studies2-4 of gas flow obeying Darcy's law have been made.' Since the partial differential equations which result from combining Darcy's flow law with the continuity equation are nonlinear, most of the published research consists of either numerical solutions or analytical solutions for linear approximating equations. Such solutions have been of limited value in field work due to their unhandy form and their failure to correlate most field data. There is evidence5,6 which indicates that Darcy's law is inadequate to describe gas flow at some flow rates of practical interest. A quadratic flow law: which reduces to Darcy's law at low rates, is more successful in accounting for experimentally observed behavior. This flow law has been applied successfully to a few hypothetical reservoir cases in work which has recently been published.10 However, these numerical solutions of the equations involved have been successful only on a special analog computer. Routine applications to field cases would be awkward and have not been attempted. The present paper describes an approximate method for computing nonsteady-state gas flow solutions which has been completely successful in predicting the results for both Darcy flow and quadratic flow obtained by elaborate numerical methods. The new calculation method allows determination of the observable variables in gas-well testing at constant rates. It is similar to the scheme of using a succession of steady states suggested by Muskat7 in that it makes use of steady-state and material-balance equations. It also is similar to the work of Aronofsky and Jenkins2 in that the new method includes Aronofsky and Jenkins' stabilized flow equation as a special case. It improves upon both of these calculation schemes in that it accurately describes all portions of reservoir history and suggests means of determining reservoir rock properties from well-test data. This paper deals only with production from a reservoir, in which case the rate is defined as being negative. The reservoir studied here is a homogeneous, disk-shaped porous body of uniform thickness, with all boundaries sealed except the inner radial boundary of the well.

Future of State and Federal Oil Regulation. BY NORTHCUTT ELY (Trans , vol 118 2400 words) The Interstate Oil Compact, ratified by six states and Congress in 1935, replaced the petroleum code, invalidated with other codes by the Schechter decision This compact endeavors, first, to conserve reservoir energy of oil pools through substantially uniform conservation measures by the states, second, it recognizes the state rather than the Federal Government as possessing the necessary police power for that purpose, third, it establishes an interstate advisory commission, so that orderly production in one state is not penalized by uncontrolled production in another, fourth, Federal interests are recognized in the control of hot oil, regulation of imports and fact-finding forecasts of supply and demand by the Bureau of Mmes It is not as complete an instrument as proposed by the Federal Oil Conservation Board in 1932, but is workable, and will be effective in proportion to the support given it by the industry Three results may follow First, now that fear of Federal control has subsided, the industry may lose interest in the compact and let it fall to pieces, second, if vigorously supported by the industry, the compact can accomplish most of the conservation objectives sought by the Federal control measures now believed unconstitutional, third, if the Compact fails, Federal regulation is almost certain to be revived, and can probably be sustained in connection with neutrality legislation, regulation of interstate pipe lines, and coordination of Federal and state gasoline taxes Nearly every step toward governmental regulation has originated within the industry state proration, the Federal petroleum code, Federal control of imports, Federal control of hot oil are examples The Compact shows a trend toward coordination between the powers of the industry, the state government, and the Federal Government If this arrangement fails through lack of interest by the oil industry, the next step is likely to be absorption by the Federal Government of the other two factors involved in the situation

Jan 1, 1937

By Carl Lemke

SOME of the principal metallurgical difficulties en-countered in the differential flotation of lead-zinc-iron sulfide ores arise from the following causes: The oxidized, or partly-oxidized, condition of one or more of the minerals ; impurities in the minerals them-selves; composition and character of the gangue miner-als; soluble salts in the ore; and unfavorable metal ratios. In many of the ores received at a custom mill there are present appreciable amounts of oxidized' or partly-oxidized minerals, although the ores may be substantially sulfides. Often the ores are not oxidized at all when received but on account of operating condi-tions at the mill it is necessary to stock them for several months before they can be milled, and considerable oxi-dation takes place while they are lying in stock. In most ores received at Midvale, when oxidation is pres-ent, the lead and iron sulfides have been more affected than the zinc sulfide, but with some ores the zinc mineral has also become partly oxidized. Some ores, such as those taken from old mine-dumps or from old stopes, may show very little total oxidation, but the greater part of the valuable minerals has been sufficiently acted upon by oxidation to make the minerals very difficult to float. Ores of this character are among the most difficult the flotation operator has to contend with, be-cause the galena, sphalerite, and pyrite are all sluggish in their behavior in the flotation cells. Only a part of the lead mineral will float in the lead circuit. The re-mainder will lag badly and tend to come up with the zinc or, if badly oxidized, will go -through all the flota-tion circuits into the tailing. The zinc mineral, if it has also been affected by oxidation, will act in a man-ner similar to the lead mineral. A hard pull will be required to float a reasonable percentage of it, and this is likely to bring up so much pyrite that it will be difficult to make a zinc concentrate of commercial grade. If it happens that the zinc mineral has not been no-ticeably affected by oxidation it will tend to float in the lead circuit because a hard pull is also required in that circuit in order to bring up the sluggish galena. When only a fraction of the sulfide minerals has become partly altered, or completely oxidized mineral is present in relatively small quantity, it is usually possible to make reasonably clean concentrates of all three sulfides, that is, lead, zinc and iron concentrates. Most of the oxi-dized and semi-oxidized minerals will go into the tailing and the losses will be proportional to the oxidation.

Jan 4, 1927

By V. R. Garfias, R. V. Whetzel

It is estimated that world consumption of petroleum, its products and related fuels during 1935 will reach an all-time peak of 1,592,000,000 bbl. —about 5.4 per cent higher than in 1934. Demand increased within the United States approximately 6.1 per cent during 1935 and in foreign countries about 4.1 per cent. The figures in Table 1 indicate that during the past five years world's production of crude petroleum and related fuels exceeded demand every year and that the aggregate difference is approximately 239,000,000 bbl. The supply in the United States exceeded consumption by some 134,000,000 bbl. over the same five-year period, while outside the United States the excess over demand is shown to be 105,000,000 bbl. Table 2 combines the excess production in the United States with its favorable balance of exports over imports, showing that the United States has reduced its storage over the five years by about 132,720,000 bbl., and indicates that, including its excess of imports from the United States, the rest of the world may have an unfavorable balance of some 371,000,000 bbl. over the five-year period. Such difference in foreign countries is largely due to increase in stocks, and partly at least remains in our imperfect knowledge of consumption statistics as an unfavorable balance. Table 3

Jan 1, 1936

By V. R. Garfias, R. V. Whetzel

It is estimated that world consumption of petroleum, its products and related fuels during 1935 will reach an all-time peak of 1,592,000,000 bbl. —about 5.4 per cent higher than in 1934. Demand increased within the United States approximately 6.1 per cent during 1935 and in foreign countries about 4.1 per cent. The figures in Table 1 indicate that during the past five years world's production of crude petroleum and related fuels exceeded demand every year and that the aggregate difference is approximately 239,000,000 bbl. The supply in the United States exceeded consumption by some 134,000,000 bbl. over the same five-year period, while outside the United States the excess over demand is shown to be 105,000,000 bbl. Table 2 combines the excess production in the United States with its favorable balance of exports over imports, showing that the United States has reduced its storage over the five years by about 132,720,000 bbl., and indicates that, including its excess of imports from the United States, the rest of the world may have an unfavorable balance of some 371,000,000 bbl. over the five-year period. Such difference in foreign countries is largely due to increase in stocks, and partly at least remains in our imperfect knowledge of consumption statistics as an unfavorable balance. Table 3

Jan 1, 1936

By E. C. Wade, R. D. Valentine

This paper describes a computer applications engineering system and it's use to apply a thermal dryer fan motor in a coal preparation plant. The computer hardware and software systems are described to indicate the general approach taken and a specific case study is reviewed to show how computer power is brought to projects in the coal industry.

Jan 1, 1983

By E. F. Miller

The subject " Safe Timbering of Working Places in Mobile Loading" is one that requires an analytical study of the strata both above and below the coal seam as well as the characteristics of the coal seam itself. The projection or mining plan must be based on economic roof control in which the application of timber can be minimized without incurring cost increases in other phases of production. The several types of loading machines in common use today are not adaptable to the same projections or timbering systems. Consequently the type of equipment to be used must also be considered. For these reasons the writer does not believe that the problems of timbering in working places can be discussed without simultaneously considering economic production as well as the safety of men and the conservation of equipment. Prior to the introduction of loading machines as a substitute for the pick and shovel system of loading coal, the care and maintenance of the individual working places were generally the responsibility of the coal loaders who worked in them. Up to that time very few coal companies had developed and applied fixed and definite standards for timbering the working places in the mines they operated. It is common knowledge that mechanical loading of coal has had several false starts in the last twenty-five years and it is only in the last decade that it has developed to the stage at which we now find it. During this twenty-five year period the management of the more responsible companies have come to realize the tremendous importance of roof control in coal mining. From a safety viewpoint, the lack of roof control has been and still is responsible for more than a third of the industry's annual fatality experience. In recent years workmen's compensation and insurance rates have steadily increased while the profit margin has decreased almost to the point of elimination. From an economic operating viewpoint, the failure to properly control roof is quite often the most costly single phase of coal mining. Since the manufacturers of loading machine equipment have so improved their machines that normal care and maintenance can reduce to a minimum the time lost because of mechanical failure the production delays from other causes have assumed a far greater importance. Roof control in the broad sense and in the light of concentrated mining plans or projections that are adapted to mobile loading should be regarded as one of the major problems in the inseparable phases of production and safety of the workman and equipment at the working face. The subject of this paper cannot be treated properly unless what is said here is based upon the broad and fundamental problem of genera' roof control. The suc-cessful solution of a problem arising in any industry must have its origin in a complete analysis of the known facts or factors that pertain to it. The several illustrations

Jan 1, 1949

By W. H. Bassett

One of the difficulties for many young engineers is the acceptance of responsibility. Even though they start as assistants to older men, they hesitate to offer positive opinions. They often make reports of observations and leave the boss to draw his own conclusions. If they happen to be in a position where they are not reporting to a senior engineer, and it is necessary to take the final responsibility for a decision, they try to get someone to help out and either assume or share such responsibility. Generally this is the result of want of confidence in one's self and fear that something may happen to go wrong and bring about criticism. Frequently diffidence is the principal factor. Young men come to me with reports on work that has been well done and well written up, who are evidently laboring under an intense desire to drop through the floor or to make a rapid' exit in some other way because of want of confidence. In my own early experience a consulting job came in that required considerable investigation. The man who was handing his place over to me mentioned my good fortune and I replied that the work would be interesting and I could handle it all right but feared the responsibility, which seemed considerable. He was an

Jan 1, 1932

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By Manuel Eissler

INTRODUCTION THE history of copper metallurgy in Japan goes back into remote ages, of this there is abundant proof, and that the working of this metal is closely connected with the artistic development of this nation is evidenced by some of the glorious monuments which have been produced by these ancient metal workers. The traveler sees to-clay in a perfect state of preservation bronze statues 150 ft. high, and over, 300 ft. in width, and 170 ft. in depth, delicately chased and beautifully marked, and when one reflects that some of them date back to the eighth century A. D., the question naturally suggests itself, how did these ancient metallurgists with their crude and primitive appliances accomplish this stupendous task? The bodies of these images are formed of bronze castings 10 to 12 in. thick, which were gradually built up and soldered together, but other pieces of magnitude, like the heads and other portions of the body are single castings. In many cases another method of construction must have been adopted. The walls of the molds were gradually built up and as the lower portion of the castings cooled, the walls were raised higher and higher and fresh metal must have been added, instead of constructing the whole mold first and then making the casting in one piece. There are still traces of substantial gilding visible on these statues, and how the pious Buddhist priests who were the constructors of them got the precious metal, is preserved in legendary tales.

Jan 11, 1914