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By Jing Li, Weiqiang Lai, Joe Zhou, Jiezhen Ma, Shuibo Chen, Ashele Copper Company, Feng Gao, Guofu Feng

"Copper-zinc ores often contain gold and silver, which can be recovered into copper concentrate by flotation as by-product. The challenges for operations that produce copper, zinc, gold and silver are the separation of copper and zinc and the low grade of precious metals. Ashele copper-zinc ore in north China contains 2.38% Cu, 0.69% Zn, 0.21 g/t Au and 18.10 g/t Ag and the plant produces copper and zinc concentrates, with gold and silver being recovered into copper concentrate. Copper occurs mainly as chalcopyrite and Zn occurs as sphalerite. Copper is well recovered with a recovery of over 94%. However, the recovery of Zn is substantially low (around 50%) due to fine grain size of sphalerite. In addition, gold recovery is much lower than expected and only 33% of gold in the flotation feed was recovered. The grade of gold in copper concentrate is also lower than the required payable grade (1.0 g/t). To determine the cause for lower Zn and Au recoveries, a plant survey program was conducted on the operation. The information acquired shows that the loss of Zn was mainly in the copper concentrates (accounting for approximately 38% of the head assay); of which, 24% was liberated, 8.5% was associated with chalcopyrite and 4.6% was associated with pyrite, indicating that the separation of copper and zinc was the main cause for the Zn loss, with liberation being the second cause for Zn loss. Future effort in improving Zn recovery should be focused on the separation of zinc from copper. Gold in the ore occurs as both microscopic gold and submicroscopic gold, accounting for 36% and 64% of the head assay, respectively. Microscopic gold occurs mainly as native gold and electrum; it is relatively coarse with a grain size of 10 to 240 µm and a large portion can be recovered by gravity. Submicroscopic gold was mainly carried by pyrite (accounting for 38%), and to a less extent, by tennantite (15%) and chalcopyrite (10%). Gold in sphalerite is nominal (1%). It is suggested that more coarse gold and tennantite be recovered and a gold recovery increase can then be achieved to obtain a copper concentrate with over 1.0 g/t Au through flowsheet optimization. Gravity concentration should be investigated and may be worth added into the existing flowsheet to maximum the gold recovery and grade.INTRODUCTIONCopper-zinc ores containing gold and silver is a subtype of polymetallic sulphide ores. Unlike porphyry copper sulphide ores and iron-oxide copper-gold ores, this type of ores often contains substantial amounts of zinc and lead. Polymetallic sulphide ores are mainly distributed in Canada, such as at the LaRonde and Horne deposits. Other examples include Mt. Morgan in Australia and Boliden in Sweden. Globally, production and reserves from gold-rich VMS deposits account for 1370 t gold. This is equivalent to 1% of the world production and reserves, whereas the Canadian total for gold-rich VMS deposits is 870 t, representing close to 10 % of Canadian production and reserves (Gosselin & Dube, 2005a, 2005b). Flotation is the principal process for processing the copper-zinc sulphides ores, for subsequent smelting, roasting, or hydrometallurgical treatment. Oxidized copper-zinc ores can also be processed using leaching technology. For example, at LaRonde operation (a Cu-Zn-Pb ore containing 3-4 g/t Au and 60-100 g/t Ag) the flowsheet consists mainly of a copper flotation circuit and a zinc flotation circuit followed by a cyanidation process of flotation tails. The precious metals are recovered with copper concentrate, zinc concentrate and cyanidation of zinc tails via Merrill Crowe precipitation (Zhou et al., 2005)."

Jan 1, 2016

By Mokka Rao, Asdrubal Serrano

"A mathematical model is developed which describes the movement of the minerals present where the vertical and angular velocities are related with the different operative parameters involved in the process of separation of silica from iron ore, which permit maximise the capacity of the spirals to obtain major productivity. The process is realised in two steps, of the rough dressing and other cleaning. Through the results obtained for chemical analysis of the final products of each spiral and the equation of movement of particles, it is proved the applicatibility and efficiency of mathematical model to operating parameters of the spiral. Moreover, it is determined though the recuperation of the final products of quality in the use spiral HC 1870 and HG 8/7. INTRODUCTIONThere is prospetive of increasing the production the iron ore in agreement with the demand of siderurgical proyects united with the external demand of quality 40 million tons per year. The Ferrominera de Orinoco Company is experimenting two types of modem spirals, Humprey (HC 1870) and Reichart (HG 8/7) which have limited capacity. For this reason this investigation designed a mathematical model with which larger units can be designed for increasing the capacity of the spiral."

Jan 1, 1999

By A. Y. Senchenko, Y. V. Kulikov

"In recent decades HPGR technology has proven itself in comminution circuits of mining plants. High technical and economic performance, lower specific energy consumption and reliability of HPGR equipment makes it an efficient alternative to conventional circuits using stage crushing and rod/ball milling, as well as to AG/SAG circuits. However, despite all the advantages of this technology the correct selection of key and auxiliary equipment is very important since errors at testing and design stages may lead to discrediting of the whole concept of HPGR application. There is a great variety of possible circuit configurations using HPGR, e.g. with circulation of edge product, with crushing of the whole discharge and circulation of screen oversize, successive two-stage crushing, etc. Each type of minerals will require its own optimal crushing circuit. In this context the testing methodology for selection of an optimal configuration becomes of prime importance. It is common knowledge that the best simulation of material crushing and softening within a HPGR can be obtained only in the course of a large-scale pilot test. The main approaches applied to this kind of testworks are described in this article. Special aspects of HPGR technology design and industrial operation are revealed as well. Some operational issues of HPGR equipment and of circuit as a whole were detected. They are related to regions specifics, plants location, and other factors. Process solutions proposed to deal with these issues are also indicated in the article. INTRODUCTIONDesign and construction of the processing plants involving High Pressure Grinding Rolls (HPGR) technology becomes more and more common in mining as this technology has specific technical and economic advantages against the circuits with autogenous/semiautogenous mills (AG/SAG) and other circuits. The main advantage of the technology is low energy consumption and low operation costs respectively. The presence of microcracks and increased content of fine size fractions in the crushed product contribute to reduction of energy required for further ball grinding. Besides, HPGR technology applies a special wear resistant liner that enables significant reduction of operation costs of grinding media and liner comparing with AG/SAG circuits."

Jan 1, 2016

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly, subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fume less fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By H. W. Gillett

Unlike most previous Howe lecturers, I had not the good fortune to be associated with Henry Marion Howe, nor to be directly one of his students. Yet, through his writings, he has been my teacher, as he has of all American metallurgists. Instructive as his writings are—I use the present tense because Howe thought so keenly and reasoned so surely, seeing clearly, as if by intuition, what was hazy to lesser minds, that his writings are still vital—it is not those books and papers, nor even the minds he trained in his classes, that were his most outstanding service. It was the spirit of Howe in his approach to the problems of metallurgy, his broad-mindedness and fairness, his recognition of the need for theories and hypotheses to explain metallurgical phenomena, his willingness to use them as servants, as well as his questioning attitude—his refusal to accept them as masters—that comprise his greatest service. This most thoroughly warrants the honor the Institute pays each year to his memory. These traits I so respect and honor in any man that I glory in this opportunity to do reverence to him in whom they were so notably united. Howe's Discussion of a Creep Problem I have often wished that Howe were still with us to turn his keen insight upon the problems of the use of metals at high temperatures, a field much studied but still very hazy. Indeed, 53 years ago, in a paper1 before this Institute, Howe stated a problem closely allied to some that still perplex metallurgists and engineers dealing with the high-temperature field. Howe was intrigued by a report2 from another old master, Robert Henry Thurston, on the behavior of annealed vs. cold-drawn iron wire, and in order to broaden the foundation for metallurgical generalization, Howe made experiments of his own on copper and silver. In these tests by Thurston and by Howe, the wires were rapidly loaded to determine the

Jan 1, 1939

By R. V. Ramani, R. Bhaskar

"While the National Academy of Sciences has stated that gravimetric sampling technology for compliance purposes is adequate, research into various aspects of respirable dust control require data on many other parameters of airborne dust. These, in turn, have created the need to use many instruments, other than personal gravimetric samplers, in mi ne environments for dust measurement. There is a need to evaluate the performance of these instruments under conditions of potential use.As part of research in the Generic Technology Center for Respirable Dust, cascade impactors, gravimetric personal samplers and gravimetric samplers collecting dust using isokinetic sampling principles were employed for dust measurements under identical conditions in a mine airway. During the course of the experiments, 8-stage cascade impactors and gravimetric samplers drawing air isokinetically were located in the center of a mine airway at various stations. Two types of data were examined - concentration of dust and size distribution of the dust collected in the samplers. The data show that the amount of dust collected by an impactor is less than half the amount collected isokinetically. The size distributions of the dusts collected from the two instruments, though comparable, show a consistent difference in median diameters. The cause for this bias is examined.The paper presents and discusses the results of the tests, including the concentrations and size distributions obtained from the two instruments for different experimental conditions. There is a need to document the performance of various dust measuring devices in mine airflow conditions.INTRODUCTIONThe sampling of airborne dust in mines can be done for several purposes. Traditionally, dust sampling has been restricted to the gravimetric measurement of airborne respirable dust to comply with the regulations governing the mining industry. Instruments such as the MRE gravimetric sampler, and personal gravimetric samplers that have collection characteristics similar to the human respiratory system have been in use for the last two decades. Presently available instrumentation for the purpose of regulation have been considered adequate by the Committee on the Measurement and Control of Respirable Dust in Mines (National Academy of Sciences, 1980),"

Jan 1, 1989

By Huleatt M, Perkin D, McLeod I, Mock C, Pratt R, Gourlay A, Timoney E, Knight N, Ward J

Generally speaking, Australia's reserves of its more important minerals (in terms of export earnings) are adequate to sustain forecast rates of production to the year 2000. The rate of forecast production increases of these commodities (aluminium - whether as bauxite, alumina or metal, black coal, iron ore and ferro-alloy minerals, base metals, tin, uranium, and mineral sands) reflects a well- ordered and sustained growth phase of Australia's mineral industry.

Jan 1, 1981

By W. M. Luff

The Brunswick No. 12 Deposit is a large polymetallic massive sulphide deposit, occurring in Ordovician age rocks of the Tetagouche Group. Silver is contained within the sulphide zones and economically it is the second most important commodity produced. Brunswick is one of the largest silver producers in Canada. The distribution of silver within the mine is presented, with examples from various levels. The concentration of silver can be shown to be related to both stratigraphy and structure. The mineralogy of silver in mill products is also presented.

Jan 1, 1986

By H F. Yu, S Ueda, J Diao, W F. Gu, Y Sasaki, H Qin

The main reason for the underutilisation of steelmaking slags is their instability, which is influenced by their complex phase structure. Recycling and sustainable steelmaking slag face challenges due to the presence of magnesium oxide (MgO), a crucial component in steelmaking slag. This study investigates the phase evolution of steelmaking slag during the cooling process with different MgO contents, using high-temperature experiments and FactSage™ software, ver 8.1, (by Thermfact/CRCT and GTT-Technologies) thermodynamic equilibrium calculations. X-ray diffraction (XRD) and scanning electron microscope - energy dispersive x-ray spectroscopy (SEM-EDS) analyses identified main phases in steelmaking slag, including Ca2SiO4 (C2S), RO (MgO-FeO solid solution), Ca2Fe2O5 (C2F), and Ca3SiO5 (C3S). The study reveals that RO phase increases as the MgO content increases. C3S precipitates from steelmaking slag with a 12 mass per cent MgO content at a reduced temperature of 1400°C. It is important to note that C3S remains in the steelmaking slag even after slow cooling. This may be due to the substitution of Ca2+ in C3S by Fe2+ and Mg2+ ions. Intriguingly, the precipitation of f-CaO in steelmaking slag with 10 mass per cent of MgO content occurred after one year, while there was no manifestation of f-CaO precipitation in the steelmaking slag with 12 mass per cent of MgO content even after one year. This discrepancy suggests a potential stabilising effect of an appropriate amount of MgO in steelmaking slag. However, it is crucial to emphasise that this inference lacks supporting data, necessitating further research to validate this hypothesis. The significance of this work is in uncovering the complexities of steelmaking slag behaviour, providing essential insights for optimising recycling processes. The research sheds light on the factors that influence the phase composition and stability of steelmaking slag, contributing to the utilisation of steelmaking slags, promoting environmental sustainability, and enhancing the overall efficiency of metallurgical processes in the current industrial landscape.

Jun 19, 2024

By Raymond M. Stateham

The Bureau of Mines evaluated temperature increases on the heads of resin-grouted bolts as indicators of the integrity of the anchoring of the bolt. Expected increases were calculated by the finite difference method; the calculations were checked by bolthead temperature measurements, both in the laboratory and in the field. The accuracy of the calculations varies with the validity of assumptions necessary to the process. Measurements in the laboratory produced a temperature rise of about 4.00 F on the head of a 4-foot bolt when installed with a full column of resin. This increase remained for about 30 minutes. Similar increases were noted on bolts installed at the White Pine mine, White Pine, Mich., but bolthead temperature increases in the mine lasted only about 10 to 15 minutes. When partial columns (reduced amounts) were used, the temperature increases were smaller.

Jan 1, 1976

By Ning Wang, Tengfei Guo, Wanyan Li, Hanjie Wen, Hannian Gu, Zehai Li

Bauxite residue (red mud) is an alkaline waste derived from the industrial process for extraction of alumina from bauxite ore. Some bauxite residues contain considerable concentrations of critical metals, for example, rare earth elements. Lithium in red mud was also reported as a potential resource. In the current study, a Li-rich red mud was leached using acetic acid to investigate the leaching behavior of lithium followed by neutralizing with hydrochloric or oxalic acid. By neutralizing red mud using diluted hydrochloric acid (0.01 mol/L), 58.04–60.27% of lithium was leached using 25% acetic acid at 95 °C for 60 min. In the meantime, more than 95% of sodium and 85% of calcium were also dissolved in the leachate solution. While oxalic acid (0.5 mol/L) was used to neutralize red mud prior to acetic acid leaching, lithium performed lower leaching efficiencies (42.41–46.88%) in comparison of using of hydrochloric acid–neutralized red mud. Nevertheless, these leaching efficiencies of lithium were close to that of calcium and much higher than those of sodium under the condition. In this study, 25% (v/v) of acetic acid, at 85 °C for 60 min, was demonstrated as optimum conditions for lithium extraction from oxalic acid–neutralized red mud using acetic acid. The results would be useful and of interest for lithium recovery and purification from red mud.

By Z. Y. Lan

Bioleaching of marmatite with various mixed cultures of microorganisms was investigated. The experiments were carried out in shaking flasks with iron-free nutrient and the pulp density of 10% wt/vol at the temperature of 30?. The results show that zinc is preferentially leached before iron. The leaching rate of zinc with the mixed culture of Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and Leptospirillum ferrooxidans is 62% in 18 days. The leaching rate of zinc with the mixed culture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans is nearly the same as that with the mixed culture of Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans (45% versus 50%). SEM and EDX analysis of the leaching residues indicate that a solid product layer composed of iron sulfide, elemental sulfur and jarosite accumulates in the mineral surface and becomes a barrier to the dissolution of marmatite. The bioleaching of marmatite follows the shrinking core product layer model. When the product layer increases and becomes insoluble, the leaching rate is controlled by the diffusion through the product layer and slows down. When the product layer decreases or becomes a porous layer, the leaching rate is controlled by chemical reaction and enhanced dramatically.

Jan 1, 2014

By D. Michaud, C. Bazin, S. Lévesque, L. Pérez-Barnuevo, H. Longuepée

In recent years, with the emergence of Geometallurgy, a great effort has been made to characterize ore resources as early and accurately as possible, to allow better design and a more efficient operation of mineral processing circuits. In this context, core logging plays an important role, since drill cores provide the first insight into the ore characteristics. However, to satisfy geometallurgical requirements, traditional core logging does not suffice. New tools and methodologies need to be developed for the automation of core logging and the acquisition of mineralogical data better related to mineral processing performances. In this paper, a methodology for the geometallurgical characterization of drill cores is proposed, based on the drill core textural patterns. Textural pattern is defined here as the macroscopic spatial arrangement of minerals. The Mont-Wright iron ore deposit (Quebec, Canada) is used as a case study. The first part of this work aimed at analyzing the potential link between the iron ores textural patterns observed in drill cores and their response to ore processing, namely comminution and concentration. Preliminary results show similar performances in terms of energy consumption and heavy liquid separation for samples showing the same textural pattern. In the second part, this work seeks to develop a methodology for the automated identification of drill core textural patterns by the application of digital image analysis and discriminant function analysis. The results obtained show that this methodology is able to discriminate between the textural patterns identified at Mont-Wright with a good rate of success. Therefore, this work lays the foundation for the development of a new drill core characterization tool, which would allow for the early prediction of the iron ore behaviour during mineral processing through the identification of drill core textural patterns.

Jan 1, 2016

By Gene Asai

Properties obtained for columbium carbide-carbon castings ranging in car-bon content from 12 to 17 weight-percent were compared with those of hot-pressed composites of similar composition. The properties were oxidation resistance in static air between 500° and 700° C, linear thermal expansion between 20° and 2,400° C, electrical resistivity between 20° and 1,500° C; microhardness between 20° and 1,500° C, and modulus of rupture between 1,300° and 1,800° C. CbC-C castings differed markedly from hot-pressed material with respect to microstructure, electrical resistivity, and modulus of rupture, but behaved quite similarly with respect to oxidation resistance, thermal expansion, and hot hardness. In oxidation resistance, thermal expansion, and hot hardness both materials were independent of carbon content. Both castings and hot-pressed composites oxidize rapidly in air above 600° C, have thermal expansion coefficients very similar to columbium metal, and the logarithm of the hardness decreases linearly with increasing temperature. The microstructures of hot-pressed composites contained varying amounts of graphite in a CbC matrix but did not contain significant amounts of a eutectic structure present in all castings, nor did they contain graphite needles which were present in the hypereutectic castings. The higher electrical resistivity of hypereutectic castings over hypereutectic hot pressings was attributed to the presence of highly oriented graphite needles in the castings. The modulus of rupture of castings was 1-1/2 to 2 times that of hot-pressed composites. Both materials displayed bend ductility above 1,800° C.

Jan 1, 1971

By V. A. Mironenko

The combined study of ground water regime and rock deformations has resulted in the theoretical substantiation of the common principles for analysis of the hydrodynamic and geomechanical processes Within the scope of unique scientific direction -hydrogeomechanics (Mironenko and Shestakov, 1974). The hydrogeomechanical models are widely used now for the analysis and forecasting the extremely important processes connected with the safe and efficient mining operations, as well as with the protection of geological medium. Among these processes are: -deformations of the open-pit slopes and spoil dumps; -consolidation of rocks due to the ground-water pressure drop; -water-end-rock material inrush into mine workings caused by deformations of the undermined rock mass; -geodynamical processes due to the changes in ground water regime; -artificial hydrofracturing in rocks; -transformations of clay linings under the tailing ponds and other technical water basins.

Jan 1, 1990

By Michael J. Miller

In the design of a modem mill, a stockpile storage system for raw and/or semi-processed ore has become almost indispensable. This paper discusses the benefits of such stockpile storage as well as the various types of belt conveyor stockpiling units available. Particular attention is given to large radial stackers since they offer the greatest flexibility. Stacker control systems and accessory equipment are briefly discussed. Various alternative reclaiming arrangements for stockpiles are reviewed and a discussion of the advantages and drawbacks of each arrangement is included.

Jan 1, 1979

By Carel Robinson

MECHANIZATION of coal mine, is radically changing the requirements for under-ground transportation. It has increased materially the need for reliability and belt conveyors are the most dependable means of moving coal away from the place where it is mined. Their record of freedom from delays is almost 100 per cent. Why then are- not belt conveyors in more general use. Part of the answer lies in the pour records made at some of the earlier installations, and in the fact that belts have so long been identified as a type of equipment suitable, in the main, only to thin seams. Another reason is lack of knowledge of the full potentialities of belt transportation.

Jan 1, 1941

By X. Cao, H. Huang, Z. Dai

"Crystal phase of copper-containing slag regulation by the slag viscosity, cooling speed and cooling method, where the slag viscosity is related to the temperature and alkalinity. According to the mineralogy properties of a copper-containing slag, experiments of crystal phase regulation and flotation were conducted. When the copper-containing slag that adding a small amount of calcium oxide was cooled slowly at a rate of 3°C/min and about 1050°C n a cinder inclusion system, the viscosity of slag can be remained under 0.25 Pa·S and more than ??% of copper particles that the grain size is larger than 20 ?m in slag. The whole flow of flotation experiment was carried out to recover copper from the copper-containing slag with crystal phase regulating and the copper concentrate grade was ?????%, the recovery efficiency of copper was 94.18%.INTRODUCTIONChina's annual output of copper slag is more than 6 million tons, the current total has reached 80 million tons. It is equivalent to 640 thousand tons of copper metal with the copper grade of 0.82%. Most of the smelting slag were storage. It is not only occupy the land and pollute the environment, but also make a huge waste of resource (Alp, Deveci, & Süngün, 2008; Carranza, Iglesias, Mazuelos, Romero, & Forcat, 2009; Gorai, & Jana, 2003), therefore, it is good way to achieve copper slag resources by the effective recovery of valuable component from copper smelting slag, which is an important measure of the current process of copper smelting slag and implement the central authorities to vigorously develop the circular economy, improve the recycling of resources, increase copper production of intensive development (Zhou, et al., 1994; Zhang, Zhang, & Wang, 2005). Currently, researches on comprehensive utilization of the coppercontaining slag made a much progress (Wei, 2004; Liu, Gai, Yang, Sui, Li, & Fu, 2008; Liu & Zhu, 2008; Zhang, 2010; Sun, Chen, & Tang, 2012; Qin, Wang, Ren, Wei, Peng, & Gu, 2012). Flotation is one of the most effective method to recover the copper from smelting slag, which has the features of low cost and high efficiency (Song & Liu, 2001; Zhang, Wang, & Li, 2012). But the copper particles in the copper smelting slag distribution is very uneven, and the thickness of the material is very serious. The copper content in the micro level is higher, the size of copper sulfide ore is less than 0.043 mm, which leads to the difficulty of the monomer dissociation (Tossavainen, Engstrom, Yang, Menad, Lidstrom, Larsson, & Bjorkman, 2007; Moustakas, Mavropoulos, Katsou, Haralambous, & Loizidou, 2012). In this study, according the process mineralogy of a smelting copper slag, the crystal of smelting copper slag was optimized by controlling the temperature, alkalinity, cooling rate and cooling method, which makes the fine copper mineral particles in the copper slag crystal further, and can be used to meet the particle size requirements of flotation, thereby enhancing the flotation of copper."

Jan 1, 2016

By A. M. Gaudin

A new method of measuring the viscosity of unstable suspensions has been developed, using a Heinz viscometer. The technique was applied to kaolin-water suspensions. Spreads in viscosity with lime additive were measured.

Jan 1, 1962

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968