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By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By André L. B. Bittencourt

The copper content in the waste slag represents the greatest loss in the process of Caraíba Metais' Smelter. By identifying the variables responsible for copper stabilization in the slag, a minimization on these losses is expected, producing a granulated waste slag with a copper content lower than 0.7%. Statistics resourses such as control charts, Pareto's diagram and correlations curves were applied for the data obtained in the first semester of 1992. The magnetite and the calcium oxide contents in the slag of the Flash Smelter Furnace were most prominent variables. Some operational changes introduced during and after this investigation have shown good results.

Jan 1, 1994

By Jorge A. S. Tenorio, Chuanwei Zhuo, Joner O. Alves, Yiannis A. Levendis

"The disposal of wastes is a serious environmental problem, since available landfill space is dwindling. Their treatment by pyrolysis or combustion has merit, and the corresponding fuel or power production is of technological interest. However, such processes need a rigid control of emissions. This work addresses the gaseous light hydrocarbons (LHCs) generated during sequential pyrolysis and partial oxidation of unserviceable tires, PET bottles, com wastes (DDGS) and sugarcane bagasse in a two-stage laminar-flow horizontal furnace, kept at 1000 °C. Gas chromatography was used to identify and quantify the components of the emitted gaseous light hydrocarbons. The results showed that the biomass residues generated the highest emissions of aliphatic hydrocarbons, whereas PET generated the most aromatic hydrocarbons. When stainless steel meshes were inserted in the exhaust flow, it was found that hydrocarbon emissions were curtailed; as such meshes catalyzed partial conversion of these carbon-bearing gases to carbonaceous nanomaterials.IntroductionLight hydrocarbons (LHCs) are volatile organic compounds, consisting of hydrogen and carbon with low molecular weight; the most common species are methane, ethane, propane, butane, etc. LHCs are valuable since they are a very important energy resource. However, uncontrolled release of light hydrocarbon gases to the atmosphere should be avoided [l, 2]. In this work, a development is presented for the evaluation of LHCs generated during the controlled pyrolysis/combustion of several wastes in a two-stage laminar-flow horizontal furnace. Samples of unserviceable tires, post-consumer PET bottles and waste residues from the bioethanol industry (DDGS and sugarcane bagasse) were burned. A catalyst system, consisting of stainless steel screens, was tested for its effects on the gaseous emissions."

Jan 1, 2011

By Varadarajan Seshadri

A physical model based on similarity principles was constructed for simulating the RH degasser of CST (Companhia Siderurgica Tubarao, Vitoria, ES, Brazil) to evaluate the circulation rate of the metal which essentially defines the degree of exposure of the metal to vacuum in the chamber and thus of the refining rate, The circulation rate on the other hand will influence the decarburization rate and removal of dissolved gases like nitrogen and hence it is essential to optimise this parameter to get maximum refining efficiency with minimum refining times, thus improving the productivity of the secondary refining process. Mixing characteristics in the ladle is evaluated by pulse tracer addition using conductivity-meters located at the down leg as well as at several locations in the ladle. The influence of gas injection through nozzles in the upleg with simultaneous bottom injection of gas as well as nozzle blockage on the circulation rates were investigated. Also simulation experiments of kinetics of decarburization were carried out using CO2 adsorption-desorption process in sodium hydroxide solution as circulating fluid and the effect of, bottom gas flow rate in this case was also evaluated. The results were carried over to prototype and to optimize the process.

Jan 1, 2003

By N. Kanari

Chalcopyrite concentrates and their pure constituents were chlorinated by C12+N2 between 25 °C and 750 °C. The reaction products were analyzed by SEM, XRD and chemical analysis. The effect of gas flow rate and chlorine content of the gas mixture on the reaction rate were investigated. At room temperature, these solids start to react with chlorine giving metal and sulfur chlorides. Complete reaction is achieved at about 300 °C and the iron and sulfur chlorides were fully volatilized. The chlorination residue is composed of valuable metals' chlorides. A simplified flow - sheet for the treatment of chalcopyrite concentrates by chlorine was suggested.

Jan 1, 1998

By Carl C. Nesbitt

A process has been developed to recover and recycle metals from wastes of brass foundries which contain copper, zinc and lead in various quantities. Tests were conducted to evaluate several leachants, including sulfuric acid, ammonia, hydrochloric acid, cyanide and acetic acid, and to determine the optimum leaching conditions, such as air flow rate, initial copper ion concentration, temperature, and agitation strength. Sulfuric acid containing copper sulfate with dissolved oxygen is the most successful leachant. More than 99% of the copper and zinc originally present in the waste was dissolved, while only 0.5% of the lead entered the solution after 14 hours of leaching. The leaching mechanisms of copper, zinc, and lead are proposed. The copper and zinc can be recovered from the solution by electrolytic processing. The unleached residue may be converted to a lead carbonate which can be converted to litharge at 400-450°C and to massicot at temperature above 500°C by calcination.

Jan 1, 1995

By W. C. Chang

Phases and magnetic evolutions of melt spun Nd9.5(Fe1-xCox)85.5B5 (x=0, 0.05, 0.1 and 0.15), (Nd1-yLay)9.5Fe85.5B5 (y=0, 0.0.5, 0.1; and 0.15) and (Nd0.95La0.05)9.5(Fe1-zCrz)81.5B9 (z=0, 0.033, 0.067 and 0.1) nanocomposites: have been investigated. It was found that a. dilute Co substitution for Fe, x=0:05-0:15, in Nd9.5(Fe1-xCox) 85.5B5 improved not only Curie temperature but also the remanence and maximum energy product. Partial substitution of La for Nd in(Nd1-yLay)9.5Fe85.5B5 may suppress the grain growth of the materials during thermal treatment. Exchange coupling between the Nd2Fe14B and a-Fe was found: to increase with increasing La content. A dilute La-substitution, y=O. 10, has proven to decrease the optimum wheel speed required for preparing melt spun ribbons with better magnetic properties; Furthermore; a slight substitution of La for Nd in (Nd0.95La0.05)9.5(Fe1-xCrx)81.5B9 nanocomposite reduced the crystallization temperature of the over-quenched ribbons and led to the formation of a multiple phases mixture. Nevertheless, a dilute Cr addition increases the Tg of (Nd0.95La0.05)9.5(Fe1zCrz)81.5B9 and also suppresses the formation of the undesired (Nd,La)2Fe23B3 and Fe3B phases: Cr was found to play an important role in grain smoothening or magnetic separation which consequently increased the Hc of Cr-containing materials.

Jan 1, 1997

By John C. Carpenter

Solvent extraction is used to selectively recover copper from iron containing sulphate solutions. As chloride ions, which form series of complexes with transition metals, are now being used for leaching. Little is known of the effects of these ions, on solvent extraction behavior. It has been shown that commercial extractants of the L1X and Kelex series extract copper from chloride media: (1) at a lower pH than from sulphate solutions, (2) to similar loadings, and (3) except for L1X 63, without transferring chloride to the organic phase. A process for selective extraction of copper from chloride solutions should thus be compatible with standard stripping and electrowinning practice. Of several diluents, differing in aromaticity, kerosene gave enhanced extraction only with L1X reagents. A change in operating temperature had little effect on equilibrium metal distribution. All the extractants examined gave adequate separation of copper from iron. L1X 63 was found to extract chloro-complexes of copper and of iron and thus transfer chloride to the organic solution. Consequently this extractant and its mixtures are not preferred for use with chloride leaching systems.

Jan 1, 1976

By Harsh Deep Chopra, Jason N. Armstrong, Susan Z. Hua

"Existence of anisotropic Curie temperature materials [E. R. Callen, Phys. Rev. 124, 1373 (1961); J. Appl. Phys. 32 S221 (1961)] is a longstanding prediction - materials that become paramagnetic at a lower temperature along certain crystal directions while remaining magnetically ordered in other directions up to a higher temperature. Validating Callen's theory, we show that all directions within the basal plane of monoclinic F e1Ss (pyrrhotite) single crystal remain ordered up to 603 K while the c-axis becomes paramagnetic at 225 K. Results prompt a re-evaluation of existing magnetic materials with a focus on magnetic characteristics along different crystal orientations above instead of below the ordering temperatures. Theoretical guidelines for identifying new materials with large anisotropy of Curie temperature are also given, and analysis protocol to characterize them in a self-consistent manner is discussed. Materials with such a large directional dependence of Curie temperature open the possibility for uniquely new devices and phenomena, including energy storage and spintronics devices.IntroductionThis paper is an overview of our recently published work on anisotropic Curie temperature materials [l]. As a background, ferromagnetic and ferrimagnetic materials are characterized by a critical temperature below which magnetic interactions prevail over thermal agitation, leading to the appearance of a spontaneous magnetization. Above this critical point, called the Curie temperature, thermal energy eventually overcomes magnetic interactions and the material becomes paramagnetic.It is less well known that the Curie temperature varies with the orientation of the crystal. In ordinary ferromagnets this orientation dependence of Curie temperature is negligible because of the vanishingly small ratio of anisotropy to exchange energy, i.e., the spherical or isotropic exchange term dominates. Thus Curie temperature in ordinary ferromagnets appears to be an isotropic property, and assigning it a single characteristic ordering temperature suffices. However, a 'small' difference is not equivalent to being the 'same', and under appropriate set of conditions the anisotropy of Curie temperature is predicted to become appreciable, as discussed in the following.In formulating the theory of 'anisotropic magnetization' [2, 3] E. R. Callen and H. B. Callen first discussed the ""interesting possibility"" of anisotropic Curie temperature [2] or ACT; Callen and Callen noted that it was W. J. Carr, Jr. who initially raised this question, and they discussed it in detail at the Conference on Magnetism and Magnetic Materials (NY, November 1960), see footnote on page 320 of Ref. [2]. Soon thereafter, E. R. Callen developed the theory underlying the anisotropy of Curie temperature and conditions conducive to its observation [4, 5]."

Jan 1, 2013

By Patricia Negrini Siqueira Poveda, Leonardo G. A. Silva

Thermoplastic materials are sensitive to ultraviolet radiation (UV), which can cause structural changes, causing variation in mechanical properties and appearance. UV range between 250 and 400 nm is considered the most aggressive to polymers, and prolonged exposure to it results in breakage and/or crosslinking chains. Light stabilizer additives, blockers or absorbers are added to the polymers for protection in order to extend the life of the final product. The choice of the adequate light stabilizer additive system depends on factors such as resin final application, thickness, geographic location of exposure, presence of fillers in the composition, contact with chemicals, among others. This study evaluates different additive systems: conventional organic, inorganic nanotechnologyc base and the synergy between them when applied to polyethylene considering carbonyl index and UV/VIS results after aging by QUV chamber.

Mar 1, 2017

By J. Y. Foley

Platinum-group elements (PGE) are preferentially associated with chromian spinels, including high-iron chromite, magnesian-chromian hercynite, and chromian magnetite in clinopyroxene-rich upper stratigraphic portions of the Tonsina ultramafic complex in southern Alaska. Ratios of Pt:Pt+Pd are proportional to chromium content in the associated chromian spinels. The maximum PGE content of geochemical rock samples from Dust Mountain is greater than 20.000 ppb (>0.6 oz/ton) with minor gold values. The maximum PGE content of tabled chromite concentrates is 3.430 ppb (0.1 oz/ton) at Dust Mountain. 1.029 ppb (0.03 oz/ton) at Sheep Hill, and 1,749 ppb (0.051 oz/ton) at Bernard Mountain. High-iron chromite at Dust Mountain yields tabled chromite concentrates with Cr:Fe ratios between 0.5 and 1.2. Lower PGE contents are found in more chromium-rich chromitites from Sheep Hill and Bernard Mountain that yield concentrates with Cr:Fe ratios between 1.0 and 2.8. Platinum-group minerals include amalgams. arsenides. PGE alloys, and sulfides. These minerals are between 3 and 40 microns in size and are concentrated along grain boundaries and fractures of metasomatically and hydrothermally altered chromian spinel grains.

Jan 1, 1987

By Taiping Lou

The effects of slag composition, additive agents, and heat treatment conditions on the perovskite (CaO ? TiO2) crystal morphology, the precipitation behavior, the crystal growth and the volume fraction (VF) in the Ti-bearing blast furnace slags were investigated. The morphology of perovskite is dispersed dendriform in molten slags. The crystal growth mechanism of the remelting of fine dendrites and the coarsening of larger grains exists throughout the solidification of molten slags. With the temperature decrease, the VF was increased and Perovskite transformed from fine dendrites to coarsening ones or equiaxed grains. The lower cooling rate can increase the VF and coarsen the grain obviously, while higher cooling rate will decrease the VF and reduce the average equivalent diameter (AED) of Perovskite. When .increasing the content of CaO and Fe20}, the VF can increase obviosly. However, high basicity will give rise to the increasing of viscosity of slag, which result in the reducing of the AED. The experimental results showed that additive CaF2 and MnO can efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promote growth.

Jan 1, 2000

By Antoine Allanore, Luis A. Ortiz, Donald R. Sadoway

"The steelmaking industry has drastically reduced its energy consumption in the last fifty years, and today’s technologies are considered to operate at their optimal efficiency with respect to energy needs. To cope with new constraints related to greenhouse gas (GHG) emissions, a change of paradigm is necessary. One of the promising technologies that could be deployed to help reach CO2 mitigation targets relies on the intensive use of electricity: molten oxide electrolysis (MOE). This paper presents the key process parameters that need to be tuned to address the practical needs for both high productivity in a steelmaking reactor and for an energy efficient process. Herein we show that contrary to common perception, the electrolysis process for ironmaking requires less energy than today’s chemical reduction route. Furthermore, we prove that most of the energy that must be provided to operate the electrolytic iron production cell is thermal energy which is readily generated by joule heating during electrolysis due to large currents being passed through the electrolyte. The energy consumption of the electrolysis cell is therefore shown to be highly dependent on the cell configuration and the chemistry of the electrolyte. As a consequence, the CO2-impact of the technology strongly depends on both the power production mode and the technological choices for design of the process, including cell configuration. Surprisingly enough, even when the electricity generation is not carbon-free, MOE still appears to be viable from the perspective of reducing GHG emissions providing sound reactor design considerations are made.IntroductionIn the context of greenhouse gas (GHG) emissions mitigation, the steelmaking industry is considering several techniques that could sustain the efforts and progress achieved by this sector in the last decades [1]. A recent report [2] on potential routes for low-CO2 steelmaking highlighted for all techniques both the strong dependency of CO2 emissions on electric power production mode and the need for a decrease in energy consumption per tonne of steel. Incited to innovate with respect to this last criterion, the steel industry considers electrolysis to be a promising technological solution, and in particular the molten oxide electrolysis (MOE) process. This process conducts electrolysis in a mixture of oxides that dissolve the iron oxide feed, which by the action of electric current is decomposed into liquid iron and oxygen gas. The opportunity for reduction in energy consumption during steelmaking by MOE is commonly attributed to the “direct” pathway from iron oxide to liquid metal offered by the use of a molten oxide melt and operation at a temperature above the melting point of iron, ideally 1600°C, to provide enough superheat for tapping the molten iron product:"

Jan 1, 2011

By Ma Shao Xian, Li Dong, Li Zhen Guo

"The new type shaft calciner ( SK-10 Serials) is developed and designed by CADRE itself on the basis of the conventional shaft calciner. The actual application in a number of calcinations plants have proven that they are of very good effect. Calcined coke calcining heated by the shaft calciner has a high quality, lower lost by fire. The shaft calciner needs no additional fuel when it is working. Anode Carbon Plant and calcined coke Plant commonly used the shaft calciner in domestic. The waste heat from the shaft calciner can be recuperated to generate electricity and to make the steam for produce. Exhaust waste heat is recovered by 90% or more. The new type shaft calciner's structure is optimized by computer simulation for fire-wall structure, combustion air to fuel ratio, volatile combustion is fully in use, furnace cooling zone structure, the exhaust smoking structure and calciner heat balance. Furnace structure and production operating parameters has been got the best optimized results. This paper introduces the working principle and characteristics of the shaft calciner - the equipment for calcining of the petroleum coke. It also demonstrates measured process parameters of the new type shaft calciner. Through comparison with the rotary kiln and conventional shaft calciner, it proves its own technical characteristics and advantages: higher capacity, high quality products, provides more energy for power generation, equipment operation and maintenance costs lower.IntroductionChina's petroleum coke market is mainly dominated by the delay raw petroleum coke. Rotary kiln and shaft calciner are the main process equipment for calcined petroleum coke. As the shaft calciner burning less, no external fuel, waste heat utilization is high, long service life, the utilization rate in China is more extensive than the rotary kiln."

Jan 1, 2012

By H. Kaffash

Ferromanganese is a ferroalloy with high manganese content which finds many uses for example as deoxidizer in steelmaking industry. However, there is very little data on the dissolution rate of carbonaceous materials in Mn containing metals. In this paper, the kinetic analysis of carburization reactions is investigated for Mn–Fe alloys. Dissolution rate of graphite in pure iron and four different alloys with 10 wt%, 40 wt%, 60 wt% and 85 wt% manganese at 1823 K was studied. Results showed that the dissolution rate of carbon from graphite increased with increasing time for all alloys. The dissolution rate constant increased with the increasing manganese content from 6.5 × 10−3 cm/s for 0%Mn to 23.6 × 10−3 cm/s for 85%Mn.

By Pengfu Tan

A thermodynamic model and computer program, CuModel, has been developed to model the distribution behaviors of Cu, Fe, S, O, Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag, copper loss in the slag, and heat balance in copper smelting process, matte converting process and copper con-tinuous smelting process. It can be predicted for any set of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxy-gen-enriched air. This model accounts for physical entrainment between matte and slag phases. It can be used in Isasmelt process, copper flash smelting process, Mitsubishi process, P-S con-verting process and Noranda process. The predictions by the present computer model are com-pared with the known commercial data from Guixi Smelter in China, PASAR Corporation in Philippines, Horne Smelter in Canada, MIM Limited in Australia and Naoshima Smelter in Ja-pan. The agreements between the computer predictions and the commercial data are excellent. In this paper, the applications of CuModel in the copper metallurgical industries have been pre-sented. CuModel has been used by Daye Smelter and Guixi Smelter in China, and by PASAR in Philippines as well.

Jan 1, 2004

By J. L. Johnson

The U.S. Department of the Interior, Bureau of Mines, investigated recovery of concentrates containing tin, tantalum, and niobium from the Kougarok deposit on the Seward Peninsula, AK. To date, 25 million lb of tin has been delineated in occurrences containing 0.36 to 1.32 pct Sn, and the resource potential is estimated to be as high as 25 million short tons at average grades of 0.75 pct Sn, 0.025 pct Ta, and 0,025 pct Nb. Deslimed ore was concentrated to 54 pct Sn, 0.3 pct Ta, and 0.3 pct Nb, with recoveries of 74 pct Sn and 44 pct Ta/Nb using a Humphrey's* spiral followed by a Deister shaking table. Tin values in the slimes were upgraded to a 5-pct-Sn concentrate using a Bartles-Mozley separator followed by flotation. The 5- pct-Sn was further upgraded by fuming to give a concentrate containing approximately 60 pct Sn. The recovery of the two products combined was 80 pct Sn and 46 pct Ta/Nb, A flowsheet with mill-design parameters resulted from the metallurgical testing. An economic analysis was made based on the proposed process.

Jan 1, 1990

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By Shenghui Guo, Ying Lei, Wei Li, Jinhui Peng, Libo Zhang, Yu Li

"Abstract: In this work, low temperature carbothermic reduction of Panzhihua low grade ilmenite after ball milling were investigated. The ball milling of ilmenite and graphite were processed in a ball mill. The milling process can attenuate the particle of ilmenite, and the ilmenite characteristic peak were broadened and weakened. The reduction temperature and behaviors are studied on the thermo gravimetric apparatus; lower temperature and higher reaction rate were obtained for the reduction of ilmenite with graphite after milled. The reduction temperature and times of ilmenite decreased to 1000-1025°C and 40-60min via milled for 4 or 8h; Low down the reduction temperature can eliminate the solution of Mg2+ and FeTi03 in a certain degree; the reduced ilmenite has an obvious loose structure, can favored the subsequent procedure such as leaching.1 IntroductionThere is about 9.66 billion tons of Vanadic Titan-magnetite deposited in Panzhihua, China. In this reserve, there is about 8.73x108 t ofTi02, Accounting for 90.54% of the Chinese reserves, and 35.17% of the international reserves and ranking first in the world. [JJ Titanium mineral deposits major classified into Rock type and Placer type. Rock type is the igneous mineral, which have great content of FeO (Relative to Fe20 3) and gangue. The rock textures are compact and almost are complex ore. Rock type Titanium mineral major are ilmenite and titan magnetite ore, difficult to separate the metal ore and gangue. l.21 Thus, the Ti02 grade of Rock type ilmenite much lower than the Placer type (Table land 11). Panzhihua ilmenite are the typical Rock-type, due to the higher contents of MgO, CaO and Si02 and the complex mineralogy in ilmenite in Panzhihua region, making its direct reduction progressively more difficult. Mechanical activation, usually carried out by energetic milling or ball milling, was reported to significantly decreased the reduction temperature and accelerate the reaction rate of reduction of ilmenite with carbon, silicon and Magnesium. f3·(>J It reported that the process temperature were decreased to 600-1000°C and the annealing time were reduced to 30-120min after milled for 50-400 h. Shorter milling time involved was imported for else procedure such as direct leaching. 171 Hardly any research had referred to the carbothermic reduction reactivity of ilmeite milled for a short time as 1-1 Oh. In the present work, the aim is to investigate the reactivity and reaction temperature of carbothermic reduction of Panzhihua ilmenite. The Phase composition and micro morphology of samples are characterized."

Jan 1, 2011

By Michael B. Tessieri

With the increasing environmental demands and higher fuel efficiency standards on auto manufacturers, the use of aluminum in automotive applications is expected to show significant growth for the balance of this decade. Cast and wrought aluminum usage is reviewed by auto part, and alloy family for the year 2000 automobile. The analysis addresses the effect of this increased volume on the recycling infrastructure and identifies issues and opportunities, which will face the recycling industry.

Jan 1, 1995