Search Documents

By Satu Strömberg

Four different nickel concentrates were oxidized in a laboratory scale laminar flow furnace in simulated flash smelting conditions. The major nickel- and iron-bearing minerals in the con- centrates were pentlandite, violarite, gersdorffite, and pyrite and pyrrhotite, respectively. Thermal decomposition, ignition and oxidation behavior of nickel and iron sulfides were examined by using optical and scanning electron microscopy. General reactivity of the concentrates was monitored with sulfur removal which was most effective in violarite-based concentrate. Pentlandite-concentrates needed higher experimental temperatures for complete desulfurization and gersdorffite-based concentrate contained 5 - 10 % of the original sulfur even in the most oxidizing conditions studied (1 100°C, 50 vol-% 02). The reactivity of the iron minerals was found to depend on the other minerals present in the concentrate. In this paper, the observed re- action products and mineralogical changes are presented and preliminary conclusions of possible reaction mechanisms of nickel-bearing minerals are discussed.

Jan 1, 1997

By L. A. Mills

After three years of experience in operating the pilot plant for the Noranda Continuous Smelting Process, the decision was made, in March 1971, to build an 800 ton per day commercial plant at Noranda, Quebec. The de- sign and layout of the plant is discussed and the installed equipment described. Experience previously gained in the pilot plant is mentioned when it has been used in the choice of equipment or plant layout. The full- scale reactor was started up in March 1973 and the operational datacollected and the experience acquired during the first 30 months of operation are described. This includes operation to produce both high grade matte and copper. Areas discussed include refractory wear, fuel consumption and throughput of copper concentrates. Changes made to original equipment and methods of operation are discussed, together with the reasons. The ad- vantages of using solid fuels to handle inert materials and to maximize converting air flowrates and concentrate throughputs are described. Relative efficiencies of oil and natural gas are compared. The addition of oxygen from a 94 ton per day oxygen plant to the reactor converting air was started in August 1975 and the initial operating results are included.

Jan 1, 1976

By Roy J. M. van Lier

In industrial aqueous solutions, germanium generally occurs in trace amounts amid high concentrations of other metals, such as zinc, copper and iron. Separation of germanium from these metals as well as its isolation from gallium and indium pose a real challenge to the hydrometallurgist. After a brief discussion of the aqueous chemistry of germanium, this paper reviews the flowsheet of the Apex Mine in Utah. The Apex property was the only mine in the world to be operated primarily for production of gallium and germanium, but apparently closed due to great operating difficulties. Several process variants proposed for the treatment of the Apex ore, including bioleaching methods, are addressed. Following a more general description of the behavior of germanium in hydrometallurgical zinc processing streams, available technology for its recovery from aqueous solutions is summarized. Precipitation, solvent extraction, ion exchange, electrowinning, ion flotation and liquid-membrane separation are all outlined in terms of the aqueous chemistry of germanium. Finally, the production of high purity germanium dioxide and metal is briefly discussed

Jan 1, 1995

By A. René Silva

The separation of Fe(III) from simulated Ni(II) solutions using different ion exchange resins was studied. The resins tested included cation exchangers with sulfonic and carboxylic groups and chelating resins with iminodiacetic, aminophosphonic, and mixed sulfonic and phosphonic groups. The dosage of resins was varied from 0.1 to 0.5 g/mL to study the impact of resin type and dosage on iron separation from simulated nickel leach solution containing 25 g/L Ni(II) and 25 g/L Fe(III) at pH 1.5. Also, the effects of different metal ion concentrations, Fe (III):Ni(II) ratios in solution, pH, and adsorption times were investigated. Experimental results demonstrate that all the chelating resins selected favored the adsorption of Fe(III) over Ni(II) with high Fe(III) loading. Soft cation exchange resins also favored the adsorption of Fe(III) over Ni(II), but no significant Fe(III) loading was observed. In contrast, strong cation exchange resins did not show adsorption preferences. The most efficient separation was observed using resin with aminophosphonic groups at resin dosage of 0.2 g/mL, having a Fe(III) adsorption over 94% and Ni(II) adsorption below 5%.

By H. Dong, J. J. Valencia, L. Nastac

"A comprehensive computer model was developed to understand and optimize the centrifugal casting process for manufacturing TiC/Al-bronze friction drums. Performance of these components requires proper distribution of TiC particles, which is shown by dimensional analysis to be dominated by centrifugal buoyancy effects and solidification kinetics.The model addresses the following: (1) a rheology-viscosity model of the interference between moving particles, (2) engulfment (entrapment) or pushing of particles in the mushy region by the advancing solid/liquid interface, (3) nucleation and growth of equiaxed and eutectic phases, (4) effects of particle size, particle concentration, and cooling rate on the final grain size, and (5) the impingement effect of particles on the nucleation and growth kinetics of solidifying microstructure.Parametric studies were conducted using the computer model to investigate the effects of various process and material parameters on the distribution of TiC particles. The effects of the volume fraction, size, and morphology of the particles (including clusters and agglomerates) on the particle distribution were evaluated in detail. The complex interaction between the solidifying structure and insoluble ceramic particles in centrifugally-cast metal-matrix-composites was also investigated.The model predictions of particle distribution and microstructure were validated with experimental data for centrifugally-cast A356/SiC and TiC/Al-bronze alloys.This work was conducted by the National Center for Excellence in Metalworking Technology, operated by Concurrent Technologies Corporation under contract No. N00140-92- C-BC49 to the U.S. Navy as part of the U.S. Navy Manufacturing Technology Program."

Jan 1, 2000

By M. Fujikawa, S. Goto, M. Nishikawa

"The semi-pilot scale plant for injection smelting of zinc calcine was operated under the committee of Joint Research Organization of Injection Metallurgy. The capacity of the plant is 10 ton metallic zinc per day. The plant was designed by the resul ts of basic and bench scale tests of the capacity of 1 ton metallic zinc per day which was published at ""Zinc '85"". The equipments of the plants, operational conditions, results of the operation such as recovery of zinc in injection furnace and condenser, combustion rate of powdered coke and consumption of energy in this process are presented in this paper. The results of the study of the feasibility of the commercial plant of 100,000 ton zinc per year by the injection smelting are also discussed in the paper. IntroductionThe research committee of new smelting process of zinc by injection was established in 1981 under the finantial support of Mining Promoting Foundation of Japan. Six zinc producing companies joined in this organization. The price of zinc was very low at that time and the energy cost, especially, cost of electric power in Japan was extremely high. Invention of a new economical process for zinc extraction had been stronglydesired. The author proposed a injection smelting of zinc as a economical process in energy saving after a calculation of thermodynamical equilibrium and heat balance(1 )(2).The research committee has been studying the injection process since 1981. The small basic experiment by using a crucible furnace was carried out from October 1981 to March 1983 and the reaction of reduction of calcine by injection smelting was ascertained (2). Vaporizatipon of zinc and behaviours of impurities were examined. After the basic experiment, the bench scale test with the production capacity of zinc of 1 ton per day was carried on from November 1983 to October 1984.The bench scale tests were carried out to obtain the proper design of feeding devices of calcines and coke into a furnace and also to obtain fundamental data for enlargement of this smelting process(3,4). The recovery of metallic zinc in this small equipments was about 50% and main loss of zinc was formation of dross in the condenser."

Jan 1, 1988

By P. A. Rusin

Many manganiferous silver deposits remain undeveloped because standard chemical extraction methods yield poor recoveries or are ' environmentally unacceptable. Biotreatment of such ore deposits in our laboratory resulted in manganese and silver recoveries of greater than 90%. Ore and sediment samples were collected from mining sites in Colorado and Arizona. Portions of samples were incubated in a semi-solid mineral salts medium amended with 20 mM glucose mid manganese dioxide (Mn medium). The cultures were incubated at 3(fC until manganese reduction was detected by a .color change fr:om .black to clear. Bacteria from these cultures were purified on Tryptic Soy Agar and individual isolates were retested for Mn reduction by an agar overlay method. Bacteria were identified according to Bergefs Manual ?of Systematic . Bacteriology. Most of the Mn-reducing bacteria are Bacillus species. Bacterial manganese reduction kinetic experiments were performed in 52 ml mineral salts broth supplemented with manganiferous silver ore instead of manganese dioiide. These cultures were incubated with agitation for 16 d. Aliquots were removed periodically and analyzed for solubilized manganese by atoniic absorption (AA). Cyanide (1,0 M) Vias added to the remaining ore-medium mixture for a 24 h bottle roll. The supernatant was analyzed for soluble silver by AA. Similar experiments were conducted on a larger scale using 15% pulp density. After bfotreatment of the ore, standard bottle rolls were performed. The pregnant solutions and the residues were analyzed for manganese and silver?using AA or fire assay as appropriate. In sterile. controls-which received no biotreatment, manganese and silver recoveries were 0.3% and 10% respectively; During biotreatment, total manganese solubilizatiori was as high as 99.8%. The reduced manganese could . be stripped from ?the growth medium using hydrometallurgical techniques. Silver recovery vaned from 70% to 92.5%. Microbial treatment of refractory mangairlferous ores can result in high recoveries of manganese and silver. Retention time varies depending upon the relative concentrations of manganese, silver, and other metals in the ore with only two days required in some cases, The biotreatment of ore is environmentally' acceptable while the use. of chemicals such as sulfur dioxide is less so.

Jan 1, 1991

By C. Dupuis

Thiourea is a promising reagent for gold extraction especially from refractory ores that cannot be treated by traditional cyanidation route. In this study recovery of gold from thiourea leaching solutions was investigated by direct electrowinning. The electrolysis cell consisted of a carbon flow-through cathode and a lead anode. The anodic and cathodic compartments were separated by a membrane. Galvanostatic mode was chosen for operation of the cell. Factors affecting recovery efficiency such as cathode thickness, linear flowrate, current intensity, thiourea and gold concentrations were investigated. The influence of some species in solution on efficiency and selectivity of recovery was investigated. Gold recovery reached 99% but current efficiency was lower than 10%. The complex formed with ferric ion and formamidine disulfide are reduced before gold-thiourea complex. Thiourea consumption occurred during leaching mainly by oxidation and reaction with dissolved copper.

Jan 1, 1989

By Hideki Minoura

"Two novel electrochemical techniques for the preparation of highly crystallized CdS film have been presented. One is cathodization of a conductive substrate in an acidic chemical bath containing cadmium salt and thioacetamide, where electroreduction of proton at small current densities induces a growth of highly crystallized CdS thin films, whose growth is not disturbed by the reactions in the solution phase. The other technique is electoreduction of aqueous Cd2+— SCN complex. An advantage of this technique lies in no formation of solid particles in the bulk, of the bath.IntroductionIn recent years much attention has been paid to materials preparation by solution processing because of its advantages in lowering the cost as well as the stress to the environment, as compared to the conventional gas phase techniques which unavoidably require high temperature and/or vacuum. We have been trying to explore novel techniques for preparing functionalized compound semiconductors by aqueous solution process. Semiconductors which we have been mainly focusing on are CdS and ZnO, which are important semiconductors finding applications in various devices. In the present paper, some of the techniques that we have recently established for the preparation of highly crystallized CdS will be presented.Methods of the CdS film processing in solution phase (wet process), which have been reported so far can be divided into two major groups; one is chemical bath deposition (CBD) in alkaline solution containing Cd2+ and thiourea 1)4) and the other is electrodeposition (ED) in acidic solution containing Cd2+ and thiosulfate ions - 5)-8) or organic solutions containing dissolved sulfur 9)-11)."

Jan 1, 2000

By Jennifer Mager, G. P. Martins, Dean Mussatti

"The role of lead, at low concentrations in high pH cyanide-electrolytes, on the dissolution behavior of gold, has been a topic of scientific and industrial concern for well over a century. The recent paper by Kondos et al [1] at CANMET (1995) this continuing interest and apparent importance. Nevertheless, the mechanism(s) by which this (and other heavy metal) component influences the electrodics of this electrochemical system has still not been unequivocally demonstrated. Instead, several plausible hypotheses, by pioneering researchers in this field, have been advanced and reiterated OVer the ensuing years. While it is generally accepted, based on equilibrium elctrode-potential calculations, that reduction (or co-reduction when oxygen is present in the electrolyte) of lead on the gold surface may occur due to cementation (contact reduction), the cemented lead has never been characterized. The work presented has reexamined the role of lead in this system, by delineating the species distribution of these system components and by interpreting the results of potentiodynamic studies in conjunction with SEM analyses of a gold electrode.1. INTRODUCTIONThe leaching of gold ores in cyanide electrolytes has been practiced for well over a 100 years. Research conducted on this topic has been primarily focused on the effects of operating parameters such as concentrations of oxygen and cyanide, and the pH of the electrolyte; or the leaching behavior of carbonaceous and sulfitic gold-bearing materials.Mechanisms by which pure gold is leached in alkaline cyanide media, with oxygen serving as the oxidant, have been subjected to continual examination and re-examination in the published technical literature during this century. Recently, it has been speculated that without the presence in the electrolyte of trace heavy metals, such as lead or mercury, that gold would not be leachable. Researchers who have tackled this topic, have either considered heavy metals to be a natural occurrence in these systems and ignored the role they may serve in the leaching process, or they have deliberately focussed on controlling their concentrations in the system to undetectable limits. As a result, conflicting findings have been reported for what would appear - depending on the details provided in these reports - to be identical systems."

Jan 1, 1997

By Frame Ritzert, Dennis Keller, Vijay Vasudevan, David Arenas

"An investigation was conducted to describe topologically close packed (TCP) phase instability as' a function of composition in the advanced ·Ni-base superalloy Rene N6. TCP phases are detrimental to overfill high-temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements. Thirty-four variations of polycrystalline .Rene N6 determined from a design-of-experiments approach were cast and homogenized at 13 l5°C for 80 hours followed by exposure at 1093°C for 400 hours to promote TCP formation. The alloys had the following composition ranges in atomic percent: cobalt 10.61 to 16.73, Mo 0.32 to 1.34%, W 1.85 to 2.52%, Re 1.80 to 2.11%, Ta 2.36 to 3.02%, Al 11.90 to 14.75%, and Cr 3.57 to 6.23%. Physical and chemical characteristics of all microstructures obtained were described using various analytical techniques. From these observations, a mathematical description of TCP occurrence (s and P phase) was generated for polycrystalline Rene N6.IntroductionNi-base superalloy single crystals represent the state-of-the-art for turbine engine airfoil application as they offer the best balance of properties to allow for the high operating temperatures required: for efficient engine operation.1 Current trends in alloy design take advantage of improved creep rupture strength with the addition .of higher levels of refractory elements. 2 In .particular, the addition of significantly higher levels of Re in third generation superalloys is key for both microstructural stability and creep rupture strength. 3 While the presence of the refractories is thought to provide strength benefits from solid solution hardening, a tendency for alloy instability in the form of topologically-close-packed (TCP) phases or secondary reaction· zone (SRZ) ·phenomena accompanies the high refractory content. 3 The formation of these phases in sufficient amount is detrimental to the overall high temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements.4 The tendency for a particular composition to form TCP may not be immediately known since the precipitation of TCP phases in Ni-base superalloys is nucleation controlled, thereby requiring long times at elevated temperatures to precipitate. 5 They preferentially nucleate along the octahedral planes of the Ni-base superalloys, usually in areas of refractory metal enrichment at grain boundaries or inside dendrites.5-6 In Rene N6, two closely related TCP phases, a and P, have been observed.2"

Jan 1, 1998

By David J. Kinneberg, Barbara E. Mangion, Arnold M. Savolainen

Analytical laboratories require a qualitative or semi-qualitative method of determining major and minor constituents in "unknown" samples to select optimal analytical techniques. This is exceedingly important in precious metal assay laboratories where the precision and accuracy requirements are exacting (routinely within 0.02%, absolute basis). This paper describes the use of an x-ray fluorescence spectrometer with a specially designed software package to select optimal analytical procedures and specify relevant analytical parameters. A wavelength dispersive XRF spectrometer is capable of quick and accurate analyses of properly prepared samples without extensive standardization. When coupled with a specially designed software package, this preliminary assay system is applicable to a wide variety of sample types including gold and silver bullion, karat gold and karat PGM alloys, high silver and high copper metallic samples as well as particulate samples of ores and sweeps. The system relieves the assayer of tedious calculations for silver inquartation and proofing, minimizes human error and standardizes selections over time. Most importantly, the system allows for independent verification of final assay results.

Jan 1, 1999

By Corby G. Anderson

Hydrometallurgical technology for the pretreatment of refractory gold concentrates has been developed at Sunshine Mining and Refining Company. It employs a patented nitrous-sulfuric acid pressure leaching process which' was proven industrially at the Sunshine refinery. Additionally, pretreatment for removal of antimony and some other impurities is done with alkaline sulfide leaching. This paper will discuss the successful application of these two technologies for pretreatment of a refractory gold concentrate prior to CIL gold recovery. A complex gold concentrate composed of pyrite, arsenopyrite and stibnite was tested. Results of antimony leaching in alkaline sulfide media will be discussed including some details of a novel and selective recovery method for gold leached by polysulfide or thiosulfate" Also, the factors important in and the results of the application of nitrogen species catalyzed pressure leaching to refractory gold concentrates will be detailed.

Jan 1, 1996

By Amy Anderson

The Silica (SME) Technology has been utilized on three separate projects focusing upon the stabilization of mercury-contaminated materials: at the Mother Lode Mine in Oregon, the Sulfur Bank Mercury Mine in California and at a former chloralkali plant in British Columbia. Each of the projects relied primarily on the results collected via EPA Method 1311 TCLP, with additional tests such as SPLP, humidity cell tests and other supporting tests employed as well. Both technical and economic performance of the silica-based technology was evaluated as well as that of competing technologies in some cases. Results established that in each of the three projects an SME chemical dosage rate of 3% chemical by weight of soil/sludge was the optimal ratio required to achieve project treatment objectives, TCLP test results exhibited a reduction in the leachable mercury from the treated materials ranging between 75% and 99% as compared to untreated material, satisfying the technical objectives for each project, Project costs ranged from $l5.00 - $18.26 per metric ton.

Jan 1, 2003

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. In this work, thc potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (DW). Seven taxa are of Alyssum genus and one of Bornmuellera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mglkg or 2.5%) and Alyssum markgrafli O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. n this work, the potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (OW). Seven taxa are of Alyssum genus and one of BornmueIIera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mg/kg or 2.5%) and Alyssum markgrafii O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By May Nyman

Due to the vast diversity of chemical media in which metal separations are executed, a wide range of ion separation materials are employed, This ,results in an ongoing effort to discover new phases with novel ion exchange properties. We present here the synthesis of a novel class at, thermally and chemically stable microporous, niobate-based materials. Ion exchange studies show these new phases are highly selective for Sr2+ and other bivalent metals.

Jan 1, 1999

By Benjamin P. Hay

Complexation of a metal ion to a ligand often results in structural changes that introduce steric strain within the ligand. A design criterior:1 for ligands that will complex metal ions more strongly is to choose Iigar:1d architecture, that minimizes this strain. This paper describes how molecular mechanics models can be used to define the degree of ligand binding site organization in terms of' ,strain energies associated with conformational reorganization and distortion of the binding conformer. This approach yields a method to predict how modifications to ligand structure will affect metal binding affinity.

Jan 1, 1999

By J. M. Skeaff

As much as 100% of the gold and 67% of the silver in a sulphur-bearing hydrometallurgical leach residue have been transferred to copper metal at copper smelting temperatures by dissolving the partially calcined residue in an iron-bearing slag maintained in equilibrium with the liquid copper metal and matte phases. The precious metals can then be recovered by conventional refining techniques. Copper can be recycled at least four times without any detrimental effects on gold and silver transfers and recoveries. Apparent copper recovery in the .process can be over 100% because of the copper content of the residue. Based on slag analys.es, the overal1 recovery of gold in the copper metal and matte phases varies from 94% to 100% under all conditions investigated. On the? same basis, silver recovery varies .from 9S% ?to 99% under optimum conditions, but is only 4S% to 73% under other, less attractive conditions. Unaccounted for silver losses of' about 30% make it difficult to determine the major factors affecting ?silver transfer and recovery. A method for implementing the technology on a commercial scale at a Canadian copper/zinc smelter has been proposed. A preliminary economic assessment and comparison of the proposed pyrometallurgical process with conventional cyanidation indicates that either process is economically attractive for recovering gold and silver from leach residues. Although the capital costs are higher, the pyrometallurgical process is simpler, has higher recoveries, lower operating costs and no .potential environmental problems related to cyanide disposal.

Jan 1, 1989

By Pingchao Ke

A crystalline polyferric sulfate (PFS) adsorbent was synthesized by oxidizing and precipitating ferrous ions under atmospheric conditions. The morphology, structure, composition and specific surface area (SSA) and adsorptive efficacy to As (III) of the adsorbent were characterized by SEM/EDS and TEM images, XRD patterns, FT-IR spectra, BET SSA analyses and adsorption experiments. The adsorbent presents as morphology of near-spherical aggregate and good crystallinity. A small amount of goethite co-precipitated with PFS in the case of the initial ferrous concentration of 1 mol/L and increased the SSA of the aggregates. The absorbent with co-precipitation of goethite showed good adsorption to As(III) and good filtering performance in the high As(III)-content solution of 10–100 mg/L under acidic, neutral and alkaline conditions (pH 2.09–9.01), and its maximal adsorption capacity and adsorption efficiency were 7911 μg/g and 96% separately. After Adsorption, the stability of the absorbents adsorbing As(III) were evaluated by TCLP tests, and the results indicated that the absorbents adsorbing As(III) were extremely stable, and the concentration of arsenic in all leaching solutions were less than 0.01 mg/L.