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By M. J. Blackburn

The phasal equilibria in TI':Al alloys has been studied Ry transmission electron microscopy, electron diffraction, and X-ray diffraction. It is shown that three-phase fields exist below the transformation, viz.: a disordered hexagonal solid solution a; an ordered hexagonal phase based on Ti3Al, aa; and a two-phase region. (a + (YZ) , occurring between the single-plzuse fields. The size. disiribution, and morphology of- the a, phase in the two-phase region is shown to be dependent upon the alloy composition and heat treatement. The ordering process in the a, phase leads to the formation of anliphase domain boundary networks; the contrast and stability of these networks is shown to be dependent on alloy composition. A new and relatively simple phase diagralil for the systemm is constructed. The phasal equilibrium at the titanium-rich end of the Ti:Al system has long been the subject of considerable controversy. crossleyl has recently reviewed the phase diagrams that have been advanced for the system and in his turn proposed yet another one. There would seem to be general agreement that a phase exists at a composition at or near Ti& with an ordered hexagonal DO,,-type structure. However, several other phases have been proposed; for instance, Ence and ~ar~olin's' diagram includes two phases, Ti2A1 and Ti3A1, in the region up to 25 at. pct Al. The position of the proposed phase boundaries varies over a considerable compositional and temperature range, a point graphically illustrated in Fig. 1 of Crossley's paper.' It is perhaps germane to briefly examine the techniques used by other workers in the establishment of the phase structure. These fall into three categories: 1) X-ray diffraction, the only limitation of which is the rather low intensity of superlattice reflections in this system.3 Thus, superlattice reflections become increasingly difficult to detect in the more dilute aluminum alloys. 2) A considerable amount of optical microscopy has been performed"2'4 and it will be shown in a later section that many of the obscure mi-crostructures that have been observed can be attributed to hydrogen contamination. It is concluded, therefore, that such observations should be interpreted with considerable care. 3) The variation of some physical property with aluminum content has been measured.5"7 These methods are a useful indication of the existence of a transformation, but are usually insufficient in themselves to identify the transformation. The results using these techniques will be considered in more detail in the discussion. In this paper, the phase structure of alloys containing up to 25 at. pct A1 has been studied by transmission electron microscopy and X-ray techniques, and the results are used to generate a new and relatively simple diagram for the titanium-rich end of the Ti:Al system. EXPERIMENTAL A series of alloys containing 5.05, 10.16, 13.39, 13.99, 14.40, 20.83, and 25.05 at. pct A1 were obtained in the form of hot-rolled sheet 0.02 in. thick. These alloys contained 0.10 to 0.15 pct 0. Thirty-gram arc-melted buttons were prepared from iodide titanium and 99.99 A1 which contained 16.1, 16.9, 18.2, 19.0, 21.6, 22.2, 23.0, and 23.9 at. pct A1 and had an average oxygen content of 0.03 pct 0. The differences in oxygen content did not appear to influence the nature of the phase transformations which were found. Oxygen content may affect the temperature of these transformations, but insufficient samples of the high-purity alloys were examined to answer this question. The heat treatment of alloys was performed in dynamic atmosphere and vacuum furnaces or in helium -filled silica capsules. A special vacuum furnace was constructed to provide a high quenching rate in which rates of 4000°C per sec were obtained using water as the quenching medium. As pointed out by Crossley,' it is important to avoid heat treatment in the a - [} phase field as the resultant segregation of the alloy into the two phases containing different amounts of aluminum can persist through subsequent treatments leading to ambiguous results. It will be demonstrated later that step cooling of specimens from the a phase region can also lead to anomalous effects. Thus, all solution treatments were carried out in either the a or 3 phase fields followed by water quenching and subsequent isothermal annealing at various temperatures. X-ray analyses were performed on a diffractometer on fine-grained bulk specimens. The value of long-range order parameter, S, wa_s calculated from the integrated intensity of the (1211) reflection. In general, the intensity of the (1011) superlattice reflection was compared with that of the (2021) fundamental reflection to correct for experimental differences between measurements. Thin foils for electron microscopical examination were produced by electropolishing using the technique described in an earlier paper.8 Dark-field techniques were employed to a large degree in this investigation using the gun-tilt method. Finally it should be noted that the lattice parameters of the D01,-type superlattice are approximately related to the disordered hexagonal phase parameters by Crf - c, and 2ad - a, where the subscripts s and d refer to the ordered and disordered unit cells, respectively.

Jan 1, 1968

By E. J. Kloos

Bureau of Mines-approved self-contained breathing apparatus of the compressed air demand type were evaluated for performance at low temperature. Apparatus durations, breathing resistances, and airflow rates were measured on machine tests at room temperature and -25° F. Man tests under actual wearing conditions verified the machine test results. Many serious functional changes in apparatus performance occurred at low temperature. Pressure regulators malfunctioned when diaphragms lost flexibility. Under certain conditions frozen condensed moisture sealed exhalation valves and fogged eyepieces. High-pressure leaks, not encountered at ordinary temperature, developed at low temperature. Tests results are discussed generally and specifically for each apparatus. Recommendations are given to obtain optimum performance from demand type breathing apparatus at low temperatures.

Jan 1, 1968

By Darrel W. Hansen

Morrow Point Dam and Power Plant are principal features of the Bureau of Reclamation's Curecanti Unit of the Colorado River Storage Project. They are under construction on the Gunnison River 20 miles east of Montrose, Colo. Johnson-MK is the prime contractor, and represents a joint venture of Al Johnson Construction Co., Minneapolis, Minn., and Morrison-Knudsen Co., Inc., Boise, Idaho. The power plant will be housed in an underground chamber in the left abutment, approximately 250 ft behind the original canyon wall. The chamber is 206 ft long and 57 ft wide. The distance from the foundation to the spring line of the roof arch varies from 51 ft in the service bay to 120 ft in the control bay. The roof arch has a rise of 16 ft. The longitudinal center line of the chamber is orientated east-west with the draft tubes discharging nearly due north. Access to the power plant chamber was possible through the cable tunnel, access tunnel, two draft tube tunnels, two penstock tunnels, exploratory tunnel, which became the ventilation tunnel, or the grouting and drainage tunnel leading to the dam. (See Fig. 1.) The shortest and fastest access was through the cable and access tunnels, and the contractor drove these two tunnels simultaneously. The cable tunnel and cable gallery excavation exposed a transverse section, at the west end of the chamber, that was 15 ft wide and extended from the crown to 5 ft below spring line. It was here that arch excavation began. The first 34 ft of advance along the arch was driven on three headings, and the muck was removed through the cable tunnel. Meanwhile, the access tunnel was completed, and a raise was driven from its crown to intersect the advancing arch excavation near the longitudinal centerline

Jan 1, 1968

By C. L. Sainsbury

Lode and placer tin deposits of the western Seward Peninsula, Alaska, have produced more than 2200 tons of metallic tin and constitute the only known domestic deposits of economic grade and size. The lode deposits consist of quartz-topaz greisens containing cassiterite and wolframite as well as numerous base-metal sulfide minerals, and most are in or near altered biotite-granite that forms isolated stocks or in rhyolitic dikes near granite. Within the main lode-producing area in the central York Mountains, nonpegmatite beryllium deposits, consisting principally of fluorite, chrysoberyl, diaspore, tourmaline, and white mica, with minor euclase, bertrandite, phenakite, hematite, and todorokite, are distributed zonally around the tin deposits and locally are transitional with them. All the known beryllium deposits are replacement lodes in carbonate rocks. In the area discussed, both tin and beryllium deposits are localized in a structural belt striking N70° to N85°E across the central York Mountains. The belt is characterized by numerous normal faults, which cut extensive thrust sheets, and by dikes of rhyolite, rhyolite porphyry, and lamprophyre that were injected along the faults. Ore deposits are localized where the dikes intrude brecciated rocks beneath thrusts and, although complex in detail, form tabular lodes that tend to lie along the thrusts. The granites contain abnormal amounts of tin, beryllium, lithium, and boron, and the tin and beryllium lodes are believed to be genetically associated with these enriched granites

Jan 1, 1968

By Charles S. Allbright

To develop a method for predicting the stability of a fuel during long-term storage from rapid aging tests at 200° F, the Bureau of Mines determined the stabilities of three gasoline base stocks and an alkylate blending stock in both sealed storage and aerated storage at 110° F for periods extending to 32 weeks. Stabilities of samples containing gasoline-additive compounds were compared by aging, using two methods--rapid aging in a bomb at 200° F for intervals up to 16 hours and storage at 110° F. The additives used were an uninhibited tetraethyllead motor mix, N,N'-di-sec-buty1-p-phenylenediamine and 2,6-di-tert-butyl-4-methylpheno1. Results were related by graphs that enable predictions of gum and sediment formation during storage from data obtained in bomb tests. A premium-gasoline base stock and the alkylate proved to be stable, but the two regular-grade gasoline base stocks were found to be unstable. Addition of the diamine antioxidant improved the stability of both of the regular gasoline base stocks, while the phenol antioxidant improved only one of them. The presence of the tetraethyllead decreased the storage stability of all four fuels, both with respect to formation of gum and precipitation of inorganic sediment. The rapid test at 200° F appears to offer promise as a basis for a method of predicting gasoline stability in long-term 110° F storage.

Jan 1, 1968

By Paul E. Melancon, Vincent C. Kelley, Dale F. Kittel

Uranium of the Grants region occurs predominantly in continental sandstones of the upper part of the Jurassic Morrison Formation, but significant lesser deposits are found in limestone of the Jurassic Todilto Formation and in black shale of the Cretaceous Dakota Formation. The deposits are disseminations that form runs ranging from a few hundred tons to several million tons. The ore consists mainly of uraninite, uraniferous carbonaceous material, coffinite, and such secondary oxidized minerals at tyuyamunite, carnotite, and uranophane. In sandstone, the ore runs were locallized by mudstone, interstitial carbonaceous material, and primary sand channel trends. In limestone, ore deposition was related to folds and fracture zones. The great bulk of production has come from the Ambrosia Lake mines in the Grants district and the Jackpile and Paguate mines in the Laguna district. The ores, which generally have been 0.20 to 0.30 per cent U3O8, are treated at mills operated by Kerr-McGee Corporation, Homestake-Sapin Partners, and The Anaconda Company, all in the Grants district. In 14·years after discovery in 1950, the deposits had yielded concentrates valued in excess of $800,000,000. Since deposition of the Jurassic host rocks, a geologic history involving tilting, faulting, erosion, changing ground-water environments, and oxidation has considerably influenced the existence and character of the deposits. It is evident that their ongm is not simple. However, a degree of agreement appears probable for a pre-Dakota age for the original ore runs, and, at Ambrosia Lake, two principal stages of ore formation, separated by Laramide faulting, are recognized. All earlier ores have been modified by Quaternary oxidation, solution, and enrichment during which time much secondary tyuyamunite, metatyuyamunite, carnotite were formed.

Jan 1, 1968

By Robert E. Barieau

A list of 163 references to original experimental PVT data on helium is presented for the period 1895 to 1968. The list is complete as of the start of the Helium Centennial Year, 1968, to the best of the author's knowledge. Citations were keypunched for easy updating and are listed alphabetically by author.

Jan 1, 1968

By H. M. Dess, S. R. Bolin

A modifiedl Czochralski technique has been utilized to grow single crystals of YVO, pure or doped with europium or neodymium, from 1 to 2 in. long and 4 to 1/2 in. in dianz. An oxyhydrog-en gas-fired furftace zuas used in this ulork, and melts were contained in iridium crucibles. Successful application of the Czochralski ~vzethod was found to depend upon atmosphere control to prevent crusting and to limit melt decomposition, the establishment of symmetrical thermal gradients in the melt to obtain stable growth, and the selection of high-quality single-crystal seeds to prevent propagation of misorientations during growth and subsequent catastrophic cracking. The suitability of YVO4 as a host for laser-active trivalent rare earth ions has long been recognized. However, the problems associated with the growth of sufficiently large, good-quality single crystals have, until quite recently, seriously hindered satisfactory evaluation of the laser potentialities of this material. Both flux growth and Czochralski growth techniques were investigated at an early stage of interest in YVO,. The former method proved incapable of yielding crystals large enough for practical use,ly2 and the latter was beset with difficulties which took some considerable time to understand and overcome. Recently, however, the Czochralski growth process for YVO, has been improved along separate but similar lines of development by groups working independently in the Crystal Products Department of Union Carbide's Electronics Division and Bell Telephone Laboratories3 so that now good-quality single crystals of satisfactory size can be produced on a routine basis. Stimulated emission from a neodymium-doped YVO4 crystal grown by the Crystal Products Department of Union Carbide was obtained by O'connor4 of MIT, Lincoln Labs. An oxyhydrogen gas-fired furnace was used in this work, Fig. 1, and melts were contained in iridium crucibles. The starting material was 99.9 to 99.99 pct pure YVO4 powder purchased from the Chemical and Metallurgical Division of the Sylvania Electric Products Co. Typical impurity levels, determined by spectrographic analyses, were as follows: Si, 50 to 500 ppm Al, Fe, Mg, 5 to 50 ppm Ni, Pb, Mo, Mn, Ce, Cs, 1 to 10 ppm Initially, YV04 powders predoped with neodymium or europium were obtained from Sylvania. Later, however, because of a desire to grow a series of crystals containing relatively broad concentration ranges of these dopants, it proved more convenient to start with pure YV04 and mechanically admix Nd2O3 or Eu@~ powders plus equimolar amounts of V2O5. The empty crucibles were preheated to 1900" to 1950oC, a temperature range where melting occurred readily. The powdered YVO4 feedstock was then added incrementally. However, a marked tendency toward

Jan 1, 1968

By John K. Hammes, Stanley D. Michaelson

Generally, the mining costs reported for the large open-pit operations in the United States and South America lie within the range of $0.20 to $0.30 per ton of material moved. (These operations have strip- ping ratios ranging from 1.5 to 4.0.) Productivities for the larger North American properties are in excess of 200 tons of material per man shift, while those for the South American operations are less than 200 tons per man shift. The most significant variations in cost are in the categories of haulage and general mine cost. Haulage costs vary, as expected, according to the mine elevation, pit profile, crusher location, and accessibility of a dump area, and general cost variations depend largely on the overhead cost items included in this category. Drilling and Blasting Practice The majority of open-pit copper mine production drilling is performed by rotary drills. Hole diameter varies from 6 in. to 12 in., with 9-in. holes being most common, and penetration rates vary from 35 ft to 60 ft per hour.

Jan 1, 1968

By J. W. Eckerd

Metal production rates of 42 to 45 tons per day were obtained with hollow-core anthracite briquets in an experimental blast furnace. Tuyere pressures were about the same for both coke and briquet operations, but from 150 to 175 pounds more of briquets were required per ton of metal than were needed with coke. Furnace operations were comparatively smooth, furnace hanging occurring less often than in previous tests with anthracite briquets. Dust production was substantially higher than with coke, however, and metal quality could not be controlled by corrective burdening and moisture control.

Jan 1, 1968

By James Boyd

Scientists and engineers must concern themselves not only with technical problems, but with the socio-economic difficulties of our scciety. The author states that raw materials are basic to the economic process and that mineral raw materials occur naturally in nearly limitless quantities. He feels that the economic pocess will provide sufficient raw materials for man's needs, and discusses in some detail the world economic environment. As our society grows in complexity, it becomes more urgently incumbent upon scientists and engineers to bring their experiences to bear on the solution, not only of technical problems, but also on socio-economic difficulties. It is to this field that I have directed a large part of my energies. RAW MATERIALS BASIC TO THE ECONOMIC PROCESS There are certain premises, frequently overlooked, which bear emphasis. As economics concerns the production, distribution, and consumption of goods, so our whole society is based on raw materials. Without the basic extractive industries of agriculture and mining, there would be no economic problems with which to deal. This principle has been expressed as "All productivity is based on three factors: 1) natural resources, whose form, place, and condition are changed by the expenditure of 2) human energy (both muscular and mental), with the aid of 3) tools.77* It seems strange that such an obvious statement needs to be made. It is forgotten by all of us, however, at one time or another when we get involved in the complicated theories of economics dealing with the financial and fiscal policies of the various governments, in the financing of enterprises, in marketing, and in labor relations. Unless decisions in all of these fields are made with this, and the rest of the "Ten Pillars of Economic Wisdom," consciously in mind, the resultant policies are doomed to eventual failure, whether these are policies of individuals, companies, or governments. The economic process is basic to society. But economics and the social aspects of humanity are inevitably intertwined. If human needs are not provided for within the basic economic structure, conflicts arise to disrupt the most carefully laid social plans. Similarly, it is the failure of society to cope with basic economic prerequisites that leads to discord within the body politic and thus to eventual economic disaster. We who are engaged in the various aspects of the mineral industry, therefore, have a large part to play in society's future development. MINERAL RAW MATERIALS OCCUR NATURALLY IN NEARLY LIMITLESS QUANTITIES Throughout my career in and out of government, I have formed my decisions on two principles: 1) Fundamentally, all mineral raw materials exist within the earth's crust in quantities greatly exceeding man's needs; 2) Any problems of supply of these materials are primarily economic in nature. With respect to my first assumption, analyses by geochemists enable them to estimate the quantities in which each of the known elements exist in the earth's crust. One of the most cautious and famous suggests that the average copper content of the lithosphere to a depth of ten miles is about 55 ppm. If this is valid, then the lithosphere contains about 1.4 quadrillion (1.4 x 10 ") tons of copper metal — an unimaginable quantity. This is 8,500,000-fold that which has been consumed by man in his existence. To illustrate further, consider that the deepest copper mine in history went to about 9000 ft below the surface; the present copper mines of the world now average less than 1500 ft in depth. We can assume that in most continental land areas of the world it is technically feasible to mine to a depth of at least one mile. The land areas of the world to an average depth of one mile, then, contain 343 billion tons (343 x 10') of copper metal, or 2000 times that which has been extracted to date. I don't believe man will ever expend his energies to extract copper from rocks which contain only a few parts per million, but he knows that each element

Jan 1, 1968

By P. S. Rudman

Crystal-structure occurrences in binary phase diagrams of fifth- and sixth-period elements, zirconium through palladium and hafniun through platinum, are surveyed with the conclusion that average .group number GN is the dominant correlative. This is interpreted in terms of curves of enthalpy differences between competitiue structures that are continuous func -tions of GN. It is further reasoned that the absolute formation energies may also be continuous functions of GN and if so can be simply obtained from the regatives of the heats of sublimation of the elements. It is shown that from such a heat of formation-GN plot the heats of mixing of alloy systems can be quantitatively predicted. For example, for sixth-period alloys very large exothermic heats of mixing are predicted for systems that span GN = 6 (i.e., Hf-Pt, Ta-Os, ...). Thermodynamic data with which to test these predictions do not appear to be available. If in the latter transition (A subgroup) elements we eliminate from consideration the fourth period where magnetic terms contribute to crystal-structure stability, as shown in Table I, there is a very regular sequence of structures. Using the group number (GN) assignments of Table I, which differ from the usual assignments of 8 to the elements listed as 8 through 10, it is perhaps trivial to say that the phase occurrence is a unique function of GN. However, the interesting aspect of alloys from among these elements is that the alloy structures also appear to correlate with GN. The GN for an alloy is given as GN = SixiGNi, where xi and GNi = atomic fraction and GN of component i, respectively. It is difficult to credit anyone in particular with having discovered this correlation, so many people have implicitly or explicitly employed it in the last 10 years. However, Bloom and Grant' in their correlation of s-phase occurrence with total number of d + s electrons were certainly one of the first to appreciate the correlation and Hume -Rothery2 appears to be responsible for the use of average GN as defined above. Only in the last few years have the phase diagrams of enough alloy systems been determined for this correlation to be surveyed with any degree of completeness. We shall here, in an abbreviated format, summarize the available phase-diagram literature and discuss some consequences of the GN correlation. BINARY DIAGRAM SURVEY In Figs. 1 to 3 the phase occurrences are summarized. In Fig. 4 the occurrence limits for the more common structures are summarized. That the GN of an alloy falls within the occurrence limits of a particular structure is a necessary but not a sufficient condition for the appearance of that structure. The preceding figures certainly illustrate that GN is a dominant correlative for structures of these elements. Many of the diagrams have complications, with ordering and other phase changes occurring in intermediate phases, that cannot be clearly accommodated in such a schematic survey and have hence been left out. Such omissions cannot, however, negate the GN correlations discussed here. Relative atomic size is also an important crystal-structure determinant and since atomic size varies quite regularly with GN for these elements it is possible that the apparent GN correlation is basically a size correlation. In Fig. 5 relative size occurrence limits are given for intermediate phases and extended terminal solutions. The relative volume, ?v/(v) - 2(vA - vB)/(vA + uB), has been taken as the measure

Jan 1, 1968

By Peter Hood

Data on world-wide geophysical activity in mining exploration programs are collected annually by the Society of Exploration Geophysicists' Geo-physical Activity Committee as part of a continuing service to the industry. The data are obtained by sending out questionnaires to all organizations which are known to be carrying out mining geophysical work; the organizations canvassed include mining companies, contractors, government departments and universities. The questionnaire is divided into three sections; namely, ground methods, airborne methods and research. The data compiled from the questionnaires show that world-wide utilization of mining geophysical methods reached a new high in 1967 with total expenditures of (U .S.) $32,323,240. This was divided as follows: ground methods, $18,106,785; airborne methods, $10,-123,405; and research, $4,093,050. For the ground methods, most money was spent on the induced polarization technique ($5,681,780); electromagne-tic methods were second in reported expenditures ($2,010,900). The total reported geophysical line mileage flown was 1,275,072 line miles, with aeromagnetic surveying being the most popular airborne method. The total amount spent on aeromagnetic surveys was $5,832,564 for 895,420 line miles. This gives an average cost of (U.S.)$6.50 per line mile.

Jan 1, 1968

By Joseph W. Martin

The Bureau of Mines investigated the backscattering of low-energy gamma rays as a method for rapidly determining the incombustible content of coal mine dust. In this method, 60-kev gamma rays from americium-24l penetrate the dust and are reflected by elements in the dust to a thin crystal scintillation detector. The number of backscattered gamma rays is proportional to the incombustible content. Tests of 40 dry, mine-dust samples containing 50 to 100 percent inert material show an average error of 2 percent. Calibration of the apparatus is necessary for each rock dust to account for variable composition. Results for samples containing more than 6 percent moisture are subject to error, but the values are lower than values obtained by chemical analysis, and thus fall on the safe side. Development of a small portable meter based on the backscatter principle appears feasible. Such a meter would find application within coal mines to check the effectiveness of rock dusting procedures.

Jan 1, 1968

ABSTRACTMechanised cut and fill stoping in the Racecourse orebodies between II and 9 levels was started in 1964.Five stopes are in progress over the two level interval, extracting the full strike length (600-2,000 ft) of each orebody without transverse pillars.Each stope is served by a central 10 ft by 12 ft service intake ventilation raise and an 8 ft by 8 ft return air raise at each end of the stope. Each stope is divided into two sections for drilling. firing. mucking, and fillingto maintain steady production. All equipment is kept in the stope for one level lift stoping. Gardner-Denver 2 boom jumbos are used for uphole drilling and Wagner ST 5 Scooptrams for loading and transport to ore passes located in the footwall of the orebody. A Wagner PTIO is used for materials handling and scaling of the stope backs.Mill tailings, after one stage of cycloning are used to fill the stope, one section at a time. About 80 per cent of the water is removed by decantation while the remainder percolates through hessian-covered pipes and boxes.The ore is passed to 11 level where it is hauled by the 3 ft 6 in. gauge train to the tipple at the shaft area. The ore is crushed underground before hoisting to the surface.A performance of about 100 ton/manshift is achieved by the drilling, blasting, and mucking crews in the stopes.

Jan 1, 1968

By Richard H. Bube

Photoelectronic radiation detectors may be conveniently classified as homogeneous intrinsic, homogeneom extrinsic, or junction type. Highly photosensitive homogeneous intrinsic photodetectors may be prepared from a number of different II-VI, III-V, or IV materials. Such materials require the presence of specific imperfections that can act as sensitizing centers to provide long majority carrier lifetime. Homogeneous extrinsic photodetectors are of interest primarity for infrared detection, and consist principully of germaniuim and silicon with suitable inpurities. A vaviety of junction photodetectors exist, with silicon us the most common material for them all. The following extrema in performance are found: 1) highest photoconductivity gain in homogeneous intrinsic photodetectors; 2) smallest response time (highest frequency response) in p-i-n junctions; 3) largest gain-bandwidth product in avalanche diodes. ALTHOUGH the total number of materials exhibiting photoconductivity effects is very large, only a relatively few of these have appropriate properties for a practical photoelectronic radiation detector. In fact if one surveys the commercial detectors currently available, one finds that the field is dominated by some ten or fewer materials. These are summarized in Table 1 in terms of the other important variable in detector fabrication, the structure of the material, i.e., whether the material is used as a single crystal or in polycrystalline form, and whether the material is used as a homogeneous detector or whether the detector depends upon the existence of a junction or barrier in the material. The principal wavelength range for each type of material is also shown, together with an indication of the utilization of intrinsic or extrinsic excitation. For the purposes of the present comparison of various detectors, it will be convenient to discuss two main topics: homogeneous photodetectors and junction photodetectors. The performance of a photoelectronic radiation detector is measured in terms of two parameters: the photoconductivity gain, and the response time of the detector. A convenient figure-of-merit is given by the ratio of gain to response time, often called the gain-bandwidth product. The photoconductivity gain is a device parameter since it varies in many cases with the applied voltage and the detector geometry, and should be distinguished from the actual photosensitivity of the material involved. This photosensitivity can be conveniently given as the product of free carrier lifetime and mobility in the material. The photoconductivity gain is defined as the number of charge carriers which pass between the electrodes per second for each photon absorbed per second, where G is the photoconductivity gain, is the pho-tocurrent in amperes, e is the electronic charge in coulombs, and F is the total number of electron-hole pairs created in the photo conductor per second by the absorption of light. The gain may also be expressed as the ratio of the lifetime of a free carrier to the transit time for that carrier, i.e., the time required for the carrier to move between the electrodes. For a material in which one-carrier conductivity dominates, where T is the lifetime of a free carrier, ttr is the transit time for this carrier, p is the carrier mobil-ity, V is the applied voltage, and L is the electrode spacing. From Eq. [2] it follows that the photoconductivity gain is proportional to the photosensitivity of the material (tP), the proportionality constant being The photosensitivity of a material, and hence the photoconductivity gain of a device utilizing the material, depends on the lifetime of the free carriers as a critical parameter. In a homogeneous material this lifetime is determined by the nature of imperfections in the material, and in an inhomogeneous material the lifetime is determined by the specific junction structure. The speed of response, the other basic photodetec-tor parameter, is determined by factors quite similar to those important for photoconductivity gain. Imperfections are of primary importance in homogeneous materials, and the structure of the junction is a determining factor in junction devices. For infrared detectors it has become common to define another quantity designed to indicate directly how effective the detector is in distinguishing between a small photoconductivity signal and random noise due to the detector and its environment. The detectivity D* is given by

Jan 1, 1968

By Sabri Ergun

This report gives the result of investigations of coals of different rank, coal com¬ponents, chemically and thermally treated and irradiated coals, and sedimented organic matter. In most studies the arbitrary parameters obtained from the usual quantitative profile analyses are not given largely because they lack physical meaning. Instead comp interpretations are offered. X-ray patterns of high-volatile bituminous and lower rank coals are not self¬-sufficient for structural interpretation by the methods of analysis developed to date. The patterns of hydrogenated and dehydrogenated coals indicate that the basic change in the structure of bituminous coals with increase in rank is the conversion of alicyclic structures into aromatic layers. In low-rank anthracites the aromatic layers are about 10 A in size. The increase in rank is the result of coalescence of layers. High-rank anthracites have layer sizes of 25 to 40 A and exhibit the development of three-dimensional (hkl) reflections of graphite, indicating ordering of adjacent layers. In meta-anthracites the layers are > 1000 A and the basic structure is that of defective crystalline graphite. The well-known petrographic components in low-rank coals have different structures; the differences dissappear in low-volatile bituminous and higher rank coals. The patterns of sedimented organic matter, except impsonites, differ from those of coal hydrogen contents are high, and their X-ray patterns are consistent with those of structures. In contrast to normal coals, the patterns of uranium-bearing coals show increased diffuseness with decrease in hydrogen content. The diffuseness is accompanied by increase in the uranium content of the coal. It is very likely that high uranium-bearing coals have predominantly tetrahedral structures.

Jan 1, 1968

By T. O. King, Y. P. Gupta

The self-diffusion of sodium in two sodium silicate liquids was measured in the temperature range 850" to 1500°C by the capillary-reservoir technique. Radioactive Na 22 was used as the tracer. The total count and autoradiographic methods were used for determination of the total Na 22 depletion and diffusion profiles of the dqy-used specimens. The diffusion coefficients obtained by the autoradiographic technique are slightly smaller than those obtained by a total count method. Error analysis of the two methods suggests that more confidence be placed in the results of the total count method. The experimental results were analyzed in terms of the existing activated rate process theory. The activation energy for diffusion was shown to decrease markedly as the temperature increased. This was attributed to a variation in the heat of activation with temperature, probably related to a change in the distribution of anions associated wilh the cation. In terms of a model, suggested for diffusion in liquid silicates, differences in the aclivation energies for diffusion and electrical conduction may arise from the effect of the electric field applied in conduction measurements. It is generally accepted that liquid silicates consist of cations and an equilibrium distribution of complex anions determined by temperature and composition. Transport properties in molten silicates are of interest, not merely because of their relevance to the kinetics of pyrometallurgical reactions and glassmak-ing processes, but also because they are useful to development of the theory of such ionic liquids. Self-diffusion is one such transport process that may, if studied for liquid silicates of widely varying compositions, indicate structural changes through changes in the activation energy for diffusion. The self-diffusion of calcium, silicon,' sulfur: aluminum, 4 and oxygenS in lime-alumina-silica melts and of iron6 in molten iron silicates have been measured. Unfortunately, the errors in some of the reported activation energies for diffusion are too large to allow firm conclusions concerning structure and the mechanism of the diffusion process to be drawn. The research reported here was a study of the self-diffusion of sodium in liquid sodium silicates. The soda-silica system was chosen since: i) a reasonable composition range can be covered in the binary system at moderate temperatures; ii) suitable isotopes of sodium (radioactive Na 22 and NaZ4) can be obtained; iii) data on the electrical conductivity and viscosity of sodium silicate liquids are available. However, the range of composition actually used in diffusion experiments was limited, to 20 to 35 wt pct soda, by the relatively high viscosity of silica-rich compositions and by evaporation of soda from basic melts. EXPERIMENTAL PROCEDURE The capillary-reservoir technique was used, wherein a radioactive tracer, Na 22, incorporated in the capillary melt, was allowed to diffuse out of the platinum capillary tube into a large reservoir of silicate liquid containing a chemically identical melt, but without radioactive tracer. After a specific diffusion time, both the total depletion in the tracer concentration and concentration-distance profiles of the diffused samples were measured by procedures to be described later. The diffusion cell assembly was similar to that used by Koros and King.' The temperature of the diffusion cell was measured with a calibrated Pt, Pt-10 pct Rh thermocouple located at the center of the liquid reservoir. The same thermocouple was used to obtain the temperature profile in the reservoir. The temperature at the top of the reservoir was slightly higher (2°C) than that at the bottom, to minimize convection in the capillary tubes, which were placed, open end up, in the reservoir. Convection was not expected to be a problem since the length-to-diameter ratio of the tubes was about 12:1 and the maximum capillary diameter was 1 mm. The diffusion cell was heated in a molybdenum-wire resistance furnace, previously used by Koros and King, but somewhat modified. A Pt, Pt-10 pct Rh thermocouple enclosed in an alumina tube and located near the furnace winding was used in conjunction with a preamplifier and Micromax proportional controller for temperature control, within 4°C, at temperatures near 1500°C. Before starting a diffusion run, the furnace was heated to the desired temperature and an alumina guide assembly for the capillaries was slowly lowered to within 2 cm of the liquid reservoir. The capillaries were thus heated to about the temperature of the bath. The run was started by lowering the assembly till the open ends of the capillaries were about 1 cm below the surface of the liquid. The run was ended by raising the assembly to about 15 cm above the liquid bath. Later, the sample assembly was slowly withdrawn from the furnace. Six diffusion samples were usually run at the same time. Three runs made with the open ends of the capillaries down were discarded because in the majority of these samples air bubbles trapped at the open end were observed. Some glass adhered to the outside of the capillary on withdrawal. This was carefully removed and used to check that the Na 22 activity in the sink remained at a low level. Materials. Nonradioactive sodium silicates were prepared by melting, in a platinum crucible, weighed quantities of sodium carbonate and powdered silica. To prepare radioactive sodium silicates, Na2 obtained in HC1 solution, was first checked for radioactive impurities by obtaining a y-ray energy spectrum, then the chloride ions were removed by anion-ex-

Jan 1, 1968

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By Glenn H. Damon

Concern about environmental pollution goes back many centuries, but until recently most efforts to control it have been perfunctory and spasmodic, aimed largely at coal smoke and other visible pollutants. Air pollution is to a large degree a byproduct of our economic development, and scientific knowledge of the causes and character of such pollution is more extensive than the technology to handle the waste byproducts of our industrial civilization. The removal of all constituents foreign to the air from the effluents produced by an industrialized society is obviously impractical at this time. There is widespread difference of opinion regarding acceptable ambient air concentration levels for the Various pollutants produced by combustion processes, but there is basic agreement that the pollution of the atmosphere must be controlled and eventually reduced. The magnitude of the air pollution problem has been increasing rapidly because our expanding economy calls for an ever-increasing consumption of energy, and fossil fuels are a principal source of energy. For example, the consumption of electricity has been increasing at an average annual rate of approximately 8 percent over the last 10 or 1.5 years. Table 1 shows the estimated emission of the principal pollutants into the atmosphere in 1966. The approximately 90 million automobiles, trucks, and buses on American highways contribute the largest proportion of pollutants to the atmosphere, but that fact does not alter the growing problems of the coal industry. You will note that sulfur oxides, particulates, and nitrogen oxides are all products of the combustion of coal. Of these air contaminants, sulfur oxides are now receiving major emphasis in terms of research to develop effective means for control, Table 2 shows that the combustion of coal produces approximately 60 percent of the sulfur oxides discharged to the atmosphere. While the utilization of coal is the principal source of particulate matter, this is not considered as serious a problem as it was in the early part of the century because of technological developments that have produced sound methods for the removal of particulates from waste gas streams.

Jan 1, 1968