INTRODUCTION

Reasons and significance of this article

In the past few decades, improvement in people living conditions led to an increase polymer consumption (mainly plastic) and its production in the last 10 years have become equal to the production during entire 20th century [1]. Under the same scenario global plastic production will increase three times by 2050 [2]. Our future generations are at risk and in order to guarantee their livings we have to put limits on profligate production by avoiding waste production and recycling the post-consumer items [3, 4]. Owing to such environmental pressures, polymer recycling is the prime focus in todays industry. Innovations in polymer waste reduction technologies under the umbrella of environmental standpoint are a difficult task, because of intricacies in reuse of polymers. However, the challenge can be overcome via establishment of optimal processes. Attention from the importance of polymer recycling cant be withdrawn as majority of these materials are non-degradable, have comparative short life cycles, distinctly visible in the waste streams ( >30% of domestic waste) and are under the great deal of public criticism . Different technological advancement has taken place in the recent years for accounting plastic waste recycling and new approaches are also under investigation [5].

Biodegradable & Non-Biodegradable polymers

Biodegradable polymers first introduced in early 1980s. Biodegradable polymers have varying sources ranging from natural polymers available in large abundance to synthetic polymers produced from nonrenewable sources. There are different processes responsible for biodegradation like chemical deterioration by living organisms or enzymatic action. Mechanism of polymer degradation has been reviewed [6]. Overall, the process occurs in two steps:

1. High molecular mass polymer is broken down into lower molecular mass species with the help of biotic reactions (oxidation, hydrolysis or photo degradation) or abiotic reactions (degradation of microorganisms). 2. Bio assimilation and mineralization of the polymer fragments by microorganisms.

Biodegradability of the polymer depends on different factors like origin of the polymer, its chemical nature and environmental conditions. Mechanical properties of biodegradable polymers is affected by their chemical composition [7, 8], processing & storage characteristics [9, 10] and application conditions [11]. Biodegradable polymers have gained attention in the past few decades due to their potential applications in the field of health and environment. However, numerous biopolymers are of market importance while others are dependent on their price level which is noncompetitive yet and need some promising development. Different methods like grafting and copolymerization have been developed to improve the physic-chemical properties of biodegradable polymers, which not only improve the rate of biodegradation but also enhance the mechanical properties of the desired product. Blending is another process which enhances morphology and physical properties of the final product. In addition, some advanced technologies including nanobiocomposites, natural fiber reinforcement, use of nanoclay and active packaging technology have also been applied [12]. Non-biodegradable materials are man-made materials which do not decompose or breakdown into simpler ones. Unfortunately these materials are not recycled at an efficient rate and causes environmental pollution. Recycling not only saves natural resources but also lower down the impact of the waste ending up in landfill throughout the world [13]. Biotechnological/ renewable production of non-biodegradable materials have also been reported e.g. production of long chain alkanes by using prokaryotic and eukaryotic organisms [14] and aromatic compounds from carbohydrates by using bacteria [15]. Moreover, persistant polymers can be

specifically produced from low molecular weight compounds e.g. ethanol and acrylamide. Ethanol obtained from carbohydrate fermentation is converted into polyethylene [16] while acrylamide is converted into polyacrylamide [17].

What are polyolefins?

Polyolefins a commodity polymers and are formed by polymerization of olefins and. They are widely spread in the whole range of polymers and play a vital role in building up nations economy due to their massive consumption volumes in industry[18]. They show resistance to biodegradation, hydrolysis and peroxidation due to the presence of stabilizers and antioxidants[19, 20]. However, adding pro-oxidants additives to them turns hydrophobic surface into hydrophilic one. Thus, a friendly environment for microorganisms is formed resulting in bio-assimilation to low molar mass oxidation products[21-25]. In European countries one third of total plastic production is polyolefins[26]. Recent economic growth in China also sparked the demand of polyolefins. In fact, the largest market of polyolefin ns in 21st century is china and pace is increasing even faster [27]. Polyolefins are essentially divided in to two classes: thermoplastics (TP) and thermosets (TS). Thermoplastics, soften upon heating (reversible process) while thermosets dont (irreversible process). Polyolefins have unlimited applications like bags, film, insulation, piping (LDPE), gas pipes (HDPE), toys, industrial wrappings, automotives and electrical components (PP) etc. Nearly 80% of the total waste comprises of thermoplastics and thermosets. Among thermoplastics polyolefins, low density polyethylene (LDPE) 17%, high density polyethylene (HDPE) 11% and polypropylene (PP) 16% are present whereas, thermosets are mainly epoxy resins and polyurethane[28]. Polyolefins contain photoinitiators and stabilizers which make them resistant to biodegradation, hydrolysis and oxidation[29]. Pro oxidant additives like Mn+2/Mn+3 can make them oxo-degradable and a free radical chain reaction results in the degradation of polyolifins by producing hydro peroxides which

are then thermolysed or pyrolysed to yield low molecular mass products with hydrophilic properties favorable to microorganisms.

Why selected Non-biodegradable

Polyolifins waste has got increased environmental concerns during the past decade. Despite significant advancement in recycling processes, major polyolifins generated waste is still disposed to landfill which is of high cost and poor biodegradability [30]. In 2002 in Europe 61% of the plastic waste generated is disposed to landfill while 39 % is recovered by using different techniques. From 2002 to 2009 energy recovery has got the higher percentage of 22% by consuming 4.7 million tons, while mechanical and chemical recycling as got 15% (3.13 million tons) and 2% (0.35 million tons) [31]. From 2009 about 60 million ton of plastic is produced but only 6% is recycled i.e. just 2% of 100 billion Euros of turnover [32]. Similarly in Greece, a low amount of 2.2 % was recovered and recycled [33]. Reprocessing of polyolefins especially PE and PP by traditional processes such as intrusion or continuous extrusion has got certain limitations like comingled plastic wastes, low product price & quality and limited market for such recycled products [34]. The Impurities like adhesives, metals, pigments and other incompatible components like polyesters and polyamides causes a low interfacial adhesion resulting in poor physic-chemical properties [35]. This indicates that recycled polymers have low value due to poor quality and there is a need for high grade polymers. Technologies to address post-consumer polyolefins should be cost effective and accurate enough to meet the purity demands. Thus, potential market for such technologies is large to valorize a substantial fraction of the materials.

Recent trends in polyolefin waste generation

Polyolefins are widely spread in the whole range of polymers and are in constant development to meet the changing demands. Recent studies has shown that avg. weight of individual packaging items is decreasing e.g. drinks bottles and PE sheets have been dropped in weight up to 15 % [36]. LDPE is most recovered polyolefin because of its abundant usage in packaging. On the other hand other polyolefins especially PP volumes are projected to increase due to increasing demands in packaging, automotive and EEE sectors. Volumes of more technical polymer waste (ABS, PA, PU) are not expected to grow substantially. The total Polyolefin waste scenario in Europe, 2005 and 2015 are described below for each waste stream [37].

Polyolefin waste scenario in Europe, 2005 and 2015

Polyolefins from waste, th. tonnes

15000 10000 5000 0 LDPE HDPE Most common Polyolefins PP 2005 2015

Fig : Estimated volumes of the most common polyolefin waste in Europe, 2005 and 2015

The production of petroleum/natural gas derivative ethylene exceeded the demand limit of 115 Mt and reached 126.7 Mt during the start of 2009 as a result of vast production in the Middle East. Thus 56% increase in Middle East raised the total production to 19 Mt and is predicted to rise to 145 Mt by 2010. On the other hand, consumption is expected to stay relatively smooth at around the current rate [38]. prior to 2008 growth in global demand figures for ethylene remained at an average annual rate of 4-

4.5% and fell by approximately 3% (about 4 Mt) in 2008. In China in 2008 production of polyethylene thermoplastic resins (LDPE, LLDPE and HDPE) consumes approximately 60% of ethylene. In the first half of 2009, PE imports to China were as were nearly equal to the imports for the whole of 2008. The import level of HDPE has seen an increase by 90% in 2009 compared to 2008 [39]. PP is a versatile and low cost Polyolefin and has a growth rate above an average of 7-8% in 2007. However, PP consumption fell to 45.5 Mt in 2008. Despite the fact that PP has beneficial properties, it is losing its competitive price position to other polymers, owing to the increase in feedstock prices [40].

Impact on socio economic life

A depletion of non-renewable natural resources would be very dangerous for the future existence of human civilization. Protection of the natural environment, a decrease of CO2 emissions and mitigation of climate change is feasible only by reducing consumption of natural resources. Therefore, a search for options to increase energy efficiency, an increase in the use of renewable energy sources and reuse of different types of waste seems to be the obvious direction of scientific activity M. Stelmachowski , K. Sowioski. THERMAL AND THERMO-CATALYTIC CONVERSION OF WASTE POLYOLEFINS TO FUEL-LIKE MIXTURE OF HYDROCARBONS Chem. Process Eng., 2012, 33 (1), 185-198 Feedstock recycling of waste raw materials (biomass, waste plastics, waste tires) is the best way to reuse primary energy and raw materials. Figure 1 shows a relationship between energy production from fossil fuels and their recovery from waste and technological similarities between these processes. This indicates also the need to develop and improve technologies of waste conversion into raw materials and/or energy.

Thermodynamic analysis based on exergy approach indicates that the best technologies to utilise waste plastics and used tires are gasification and thermal degradation (cracking and pyrolysis) (Fratzscher and Stephan, 2001; Stelmachowski, 2010a). These technologies ensure the highest rate of recovery of primary energy. Fratzscher W., Stephan K., 2001. Waste exergy utilisation An appeal for an entropy based strategy. Int. J. Therm. Sci., 40, 311-315. DOI: 10.1016/S1290-0729(01)01222-4. Stelmachowski M., 2010a. Thermodynamic analysis and modeling of the process of thermal and catalytic convertion of waste polymers into liquid fuels and electricity. Polish Academy of Sciences Branch in Lodz, the Environment Committee (Polska Akademia Nauk Oddziaw odzi, Komisja Ochrony rodowiska), d, 2010. ISBN 978-83-86492-60-2 (in Polish). Waste plastics contribute to many environmental and social problems due to the loss of natural resources, environmental pollution, depletion of landfill space and demands of an environmentally oriented society. The advantages of plastics (such as lightness, sturdiness, chemical resistance, and low cost) that make them suitable for an enormous number of practical uses simultaneously are their disadvantages due to their impact on the environment. Chemical resistance and sturdiness result in long time of natural decomposition, low price brings out low profitability of recycling and low weight contributes to the fact that scrap plastics take up a large volume. The consumption of plastics per capita differs very much in the world even in developed countries. In Europe, the consumption of plastics was about 24-150 kg/person in 2003-2005, while 10 years earlier the average consumption in the EU had been about 20-60 kg/person (Aguado et al., 2008; Spokas, 2008; Stelmachowski, 2010a). Aguado J., Serrano D. P., Escola M. J., 2008. Fuels from waste plastics by thermal and catalytic processes: A review. Ind. Eng. Chem. Res., 47, 7982-7992. DOI: 10.1021/ie800393w. Spokas K., 2008. Plastics still young, but having a mature impact. Waste Management, 26, 473-474, DOI:10.1016/j.wasman.2007.11.003.

Stelmachowski M., 2010a. Thermodynamic analysis and modeling of the process of thermal and catalytic convertion of waste polymers into liquid fuels and electricity. Polish Academy of Sciences Branch in Lodz, the Environment Committee (Polska Akademia Nauk Oddziaw odzi, Komisja Ochrony rodowiska), d, 2010. ISBN 978-83-86492-60-2 (in Polish).

The amount of waste polymers increases by 6.6 to 12% each year, depending on the country. Waste plastics represent only 7 to 9% of total waste in terms of mass but about 30% in terms of volume. About 70% of waste are polyolefin, including polyethylene (PE), polypropylene (PP) and polystyrene (PS). The majority of these waste are disposed in landfills or incinerated (2025%), with no attempt to recycle using of chemical recycling or thermal degradation processes (Scheirs and Kaminsky, 2006; Williams and Slaney, 2007). Scheirs J., Kaminsky W., (Eds.) 2006. Feedstock recycling and pyrolysis of waste plastics: Converting waste plastics into diesel and other fuels. Wiley Series in Polymer Sciences. John Wiley & Sons, Ltd, Chichester. Williams P.T., Slaney E., 2007. Analysis of products from the pyrolysis and liquefaction of single plastics and waste plastic mixtures. Resour. Conserv. Recycl.,51, 754-769. DOI:10.1016/j.resconrec.2006.12.002. In the near future, a disposal of organic waste and plastics in landfills will be almost impossible due to the law, high costs and growing ecological social awareness. However, there are also some technological and economic constraints that limit full and efficient recycling of waste plastics into useful products.

General recycling procedure

Recycling is a complex method of environment protection, which aim is the limitation of the raw materials consumption and decrease of waste quantity. It should be a multiple system of the same materials using in the next material and usable goods. In the literature, there appears many definitions

of recycling. Recycling is reprocessing of old materials into new products, with the aims of preventing the waste of potentially useful materials. Another meaning of recycling is taking a product or material at the end of its useful life and turning it into a usable raw material to make another product. In accordance with Act on Waste recycling shall mean recovery which involves re-processing of substances or materials included in waste in the manufacturing process in order to obtain substances or material of original or other designated usage, including also limited recycling, excluding energy recovery [1].

In practice, recycling is often the necessity and it always becomes the only reasonable strategy of the working if consider waste formation in the End of Life phase EoL [2]. Every product has to be designed, produced, sold, consumed or exploited and every product, after time, doesnt satisfy the needs because of the physical or moral consumption [2, 3]. It becomes waste. The EoL analysis leads to resources sustainment model. Product recovery as an elongation of product life cycle can concern the whole products, theirs components and materials and raw materials, generally recovered value. The basic possibilities of recovery: reuse, remanufacturing, reclaim, recycling (Fig. 1)

The most beneficial and durable way of waste problem solution is avoidance of waste formation. The healthy for the environment life style, goods consumption and waste treatment promotes 3R principle.

The first principle (Reduce) reminds about possibility of waste quantity reduction by limitation of unnecessary products consumption.

The second one (Reuse) takes into consideration a possibility of products reuse which are generally recognize as disposable. It decreases environment pollutions scale which are formed during technological process or waste accumulation.

The third principle (Recycle) speaks that not all waste can be avoidance like not all kinds of products can be repeatedly usage.

The recycling stages consist of initial and secondary processes. To the first one include:

sorting and separation washing;size reduction pressing briquetting and granulation.

The secondary processes consist of [4, 5]: composting of solid waste (biological processing); combustion and pyrolysis (thermal processing); biogas generation (biochemical processing); electrochemical metals recovery (electrochemical processing).

Waste processing technologies containing the secondary processes make possible waste utilization on the basis of methods: Chemical recycling; resources recycling; thermal recycling; material recycling

biological recycling.

[1]Act on Waste of 27 April 2001. [2]A. Hamrol, P. Wiegandt, Enlarged life cycle of product, Cleaner Production in Poland 6 (2000) 12-15 (in Polish). [3]M. Dudek-Burlikowska, D. Szewieczek, Quality estimation methods used in product life cycle, Journal of Achievements in Materials and Manufacturing Engineering 24/2 (2007) 203-206. [4]B. Bieda, The role of thermal treatment in an integrated waste management, Proceedings of International Conference Waste Recycling, Cracow, 2005, 104-113. [5]P. Vindis, B. Mursec, C. Rozman, M. Janzekovic, F. Cus, Biogas production with the use of mini digester, Journal of Achievements in Materials and Manufacturing Engineering 28/1 (2008) 99-102.

Magnetic density separation

The standard route of processing ore or waste to high grade materials is to first liberate the various materials that are present in the feed by crushing, milling, cutting or shredding. Then, the resulting flow of particles is classified with screening, into narrow size fractions to improve the final separation. Density separation is used on a large scale in the beneficiation of ore and waste. Methods that use solely the density differences of materials are successful because the separation is, in principle, not influenced by size or shape of the materials, resulting in high grade products. Unfortunately, conventional methods have limitations in the density that can be reached.

E.J. Bakker*, A.J. Berkhout, L. Hartmann and P.C. Rem. Turning

Magnetic Density

Separation into Green Business Using the Cyclic Innovation Model. The Open Waste Management Journal, 2010, 3, 99-116
The MDS setup, which has been built up, consists of injection zone, laminator, separation zone and product collection zone (Fig. 2). The separation is a complex mix of fluid dynamics, particle-particle interactions and magnetic separation forces. Particles of polymers are easily packed so that poor separation behaviour will be shown. For this reason, the mixture of wetted particles is mixed with the process fluid in a turbulent flow, which disperses the various materials over the cross-section of the channel. However, entering the magnetic separation zone, the fluid must become as laminar as possible in order to let the magnetic forces create the separation without turbulence. Hence, the flow of the

process liquid and the movement of the particles are essential for simulation, especially in the separation zone. A model of the separation zone has been done (Fig. 3). By continuously comparing the simulation and experiments, the design of the MDS setup will be optimized. And the simulation must give multiple answers in order to have sufficient flexibility for the elaboration of the final design.

Fig. (2). Medium Density Separation (MDS) setup.

One of the major opportunities is the recycling of polyolefin waste. Polyolefin fractions are often end fractions resulting from the recycling of cars, waste from electric and electronic equipment (WEEE) and packaging waste. Sinkfloat with water as the medium is the most commonly used process that creates mixtures of PP and PE as a float fraction. Typically, the PP:PE ratio ranges from 70:30 for car scrap to 25:75 for packaging waste. Such mixtures can be disposed in a safe way or used for energy recovery. A third option, reusing the mixture for consumer products, can only be possible after mechanical recycling. When reusing it as a high quality product the grade of PP and PE should be better than 97%. Which of the three options is preferred should be determined by a Life Cycle Analysis. When opted for mechanical recycling, MDS is one of the promising techniques [11]. E. J. Bakker, P. C. Rem and N. Fraunholcz, Novel method to separate polyolefins from sredder residue based on inverse magnetic density separation, Proceedings of the 6th IdentiPlast biennial conference on the recycling and recovery of plastics, 2007. In order to produce high-purity granulate from complex streams of post-consumer waste, of a quality comparable to materials presently produced from post-industrial waste, a separation technology is needed that is sensitive to very small differences in the physical properties of the materials.

At the same time, in order to be economically and ecologically sound, the process should recover most of the polyolefins into useful products and minimize process residues. Current available separation technology is mainly based on a accurate identification of the primary plastic contained in a particular item, followed by some type of manual or automated sorting are essential [1]. In the case of plastic bottle sorting, automated selection procedures, commonly based on optical-sensing-techniques (OST) can be applied. They are not so successful because of the different bottles size and shape characteristics. Furthermore the presence of labels, surface contamination, presence of paint and coating, represent an other obstacle in the utilisation of OST. Another wide applied sorting strategy is based on density. Also this approach is not particularly helpful, especially to perform a very strict separation. Most plastics, in fact, are very close in density (HDPE = 0.941 g/cm3, MDPE = 0.9260.940 g/cm3, LDPE = 0.9150.925 g/cm3, LLDPE = 0.910.94 g/cm3, PP = 0.96 g/cm3). In the case of rigid plastic rigid waste, resulting from electronic parts, a heavy medium separation is usually applied [2]. This can be done by adding a modifier to water or by using tetrabromoethane (TBE). However, this is a costly process and can lead to contamination of the recovered plastic [2, 3]. Hydrocyclones can represent a good tool to strength density separation efficiency. Hydrocyclones, which use centrifugal force, enhance material wettability. Some of the factors affecting liquid separation of a given plastics material are: i) degree of wettability, ii) variation in density, related to polymeric structure, fillers materials utilised, typologies of pigments, etc., iii) morphological and morphometrical characteristics of plastic particles as they result from comminutionclassification processes, iv) degree of liberation of one polymer in respect of another one or to other non-plastics materials. The presence of air bubbles attached to plastic particles produce different negative effects of specific plastic recovery, that is: i) a reduced wetting of the surface and ii) a floating of the particles due to the fact that the system airplastic flake float in a solution less dense than that of bulk material [4].

Triboelectric separation, which can distinguish between two resins by simply rubbing them against each other, is another sorting strategy currently applied to separate plastics. A triboelectric based separation device sorts materials on the basis of a surface charge transfer phenomenon. When materials are rubbed against each other, one material becomes positively charged, and the other becomes negatively charged or remains neutral. Particles are mixed and contact one another in a rotating drum to allow charging. Materials with a particle size of approximately 24 mm were the highest in both purity and recovery in the triboelectric process [5]. Plastic solid waste can also be sorted by a speed accelerator technique, developed by Result Technology AG (Switzerland). This technique uses a highspeed accelerator to delaminate shredded waste, and the delaminated material is separated by air classification, sieves, and electrostatics [2]. Using X-ray fluorescent (XRF) spectroscopy, different types of flame-retardants (FRs) can be identified. On this basis, MBA Polymers, Inc. has developed a technology that can separate pure resin with FRs [6, 7]. W2Plastics is applying the emerging technology called Magnetic Density Separation (MDS) [8] to separate the various types of Polyolefins: polypropylene (PP), low density polyethylene (LDPE) and high density polyethylene (HDPE), from each other and from contaminant materials such as wood, rubbers and minor amounts of metals and foams. MDS technology is potentially very cheap because it separates a complex mixture into many different materials in a single process step, using one and the same liquid. The entire separation is performed as the mixture flows through a channel and segregates in a few seconds into as many different layers as there are products. The water-based W2Plastics is applying the emerging technology called Magnetic Density Separation (MDS) [8] to separate the various types of Polyolefins: polypropylene (PP), low density polyethylene (LDPE) and high density polyethylene (HDPE), from each other and from contaminant materials such as wood, rubbers and minor amounts of metals and foams. MDS technology is potentially very cheap because it separates

a complex mixture into many different materials in a single process step, using one and the same liquid. The entire separation is performed as the mixture flows through a channel and segregates in a few seconds into as many different layers as there are products. The water-basedprocess liquid is recovered mechanically to the point that only about 5 kg of liquid remains per ton of de-watered product. Since each kg of process liquid contains as little as 6 grams of iron oxide (the active material for the separation), most applications of the polyolefin products do not require that such a minor amount of liquid need to be washed from the plastics. Therefore very low costs are associated with the recycling and quality control of the liquid, usually one of the expensive steps in advanced sink-float separations. MDS is also potentially very sensitive to small differences in material density, provided that the turbulence in the liquid can be accurately controlled. Preliminary results obtained with a small MDS laboratory setup have shown that PP could be separated cleanly from PE. [1] S. M. Al-Salem, P. Lettieri and J. Baeyens, Recycling and recovery routes of plastics solid waste (PSW): A review, Waste Manag., vol. 29, pp. 2625-2643, December 2009. *2+ H. Kang and J. M. Schoenung, Electronic waste recycling: a review of U.S. infrastructure and technology options, Resour. Conserv. Recycl., vol. 45, no. 4, pp. 368-400, March 2005. *3+ H. M.Veit, C. Pereira and A. M. Bernardes, Using mechanical processing in recycling printed wiring board. J. Minerals Metals Mater. Soc., vol. 54, no. 6, pp. 45-47, January 2002. *4+ American Plastics Council (APC), Development of hydrocyclones for use in plastic recycling. Technical paper, 1999. *5+ C. Xiao, A. Laurence and M. B. Biddle, Electrostatic separation and recovery of mixed plastics. In: Society of Plastics Engineers (SPE) Annual Recycling Conference (ARC), Dearborn, Michigan (US), 1999. *6+ S. Toloken, Computers, plastics dont mix well. In: Waste news; June 1st. Available at: http://www.wasterecyclingnews.com/arcs how, 1998. *7+ American Plastics Council (APC), An industry full of potential: ten facts to know about plastics from consumer electronics. Technical paper, 2003. [8] E.J. Bakker, P.C. Rem, N. Fraunholcz, Upgrading mixed polyolefin waste with magnetic density separation, Waste Management, vol. 29, no. 5, pp. 1712-1717, June 2009.

Triboelectric separation
Whenever two materials of different nature are subjected to either a simple contact or a friction test, electrical charges are generated and exchanged between them. This phenomenon has been known as the triboelectricity [1-4]. Triboelectricity is attributed to the electron transfer from one body to another [5-8]. However, in some specific cases (especially involving polymers), its shown that the triboelectric chargecreated on the surfaces of particles may be the result of a ions transfer [9] or mass transfer [10]. In some systems, the three mechanisms of charge transfer can occur simultaneously [7]. The electrostatic separation methods such as coronadischarge and electrostatic induction can separate mixtures of metals/insulators, whereas the triboelectrostatic method is specific for separating variousmixtures of insulator/insulator particles [11-13]. Industrial applications of triboelectrostatic separation are numerous. The most important are thetreatment of ash from coal power plants [14-17] andseparation of granular plastic mixtures in the recycling [18-19]. In triboelectrostatic separation, the charged particles separate through an electric field by the particle particle and particlesurface charging mechanisms. The charging method and charge density (nC/g) of the plastics have beenreported by various researches. Many studies have been performed to analyze performance of triboelectric separators forsorting different types of insulating particles. There are currently several methods of triboelectric charging using rotating tubes [20-22], fluidized beds [23-28], a vibrating feeder[29-30], tribo-cyclones [31-32], fans [33-34], static charger, a honeycomb and a spiral tube charger. [1] W. R. Harper, Contact and Frictional Electrification, London: Oxford University Press, 1967. [2] J. Lowell, "Contact electrification of metals," J. Phys. D: Appl. Phys, vol. 8, p. 53-63, 1975. [3] L. B. Loeb, Static Electrification, Springer, Berlin, 1958. [4] D. K. Davies, "Charge generation on dielectric surfaces," J. Phys. D: Appl. Phys., vol. 2 , p 1533-1537, 1969. [5] E. G. Kelly, and D. J .Spottiswood, "The theory of electrostatic separation: a review," part II. Particle Charging. Miner Eng, vol. 2, p. 193-205, 1989.

[6] C. Pounder, "The Quest for a Charging Mechanism to the End of the 19th Century," J. Electrostatics,vol. 3, p. 389-394, 1977. [7] G. S. P. Castle, "Contact Charging Between Insulators," J. Electrostatics, vol. 40-41, p. 13-20. (1997) [8] S. Mazuda, M. Toragushi, T. Takahashi, and K. Haga, "Electrostatic beneficiation of coal, using a cyclone-tribocharger," IEEE Trans.Ind. Appl., vol. 19, p. 789-793, 1983. [9] A. M. Gaudin, "The Principles of Electrical Processing with Particular Application to Electrostatic Separation" Miner. Sci. Engng., 3, 46-57. (1971) [10] W. R. Salanek, A. Paton, and D. T. Clark, "Doublemass transfer during polymer-polymer contacts," J. Appl. Phys., vol. 47, p. 144-147. 1976. [11] E. G. Kelly, and D. J. Spottiswood, "The theory of electrostatic separations: a review," part I. Fundamentals, Miner Eng, vol. 2 p. 3346, 1989. [12] A. Tilmatine, S. Bendimerad, M. Younes, and L. Dascalescu, "Experimental analysis an d optimisation of a free-fall triboelectric separator of granular plastic particles," International Journal of Sustainable Engineering, Vol. 2, No. 3, p.p. 184191, Sep. 2009. [13] A. Tilmatine,S. Bendimered, F. Boukhoulda, K. Medles, and L. Dascalescu, "Electrostatic separators of particles.Application to plastic/metal, metal/metal and plastic/plastic mixtures," Waste management, Elsevier, 29, p.p. 228232, 2009. [14] P. Carbini, M. Carta, R. Ciccu, C. Del Fa, M. Ghiani, and G. Rossi, "Beneficiation methods for coal desulphurization," 64th Proc. CIC Coal Symp, 1982. [15] D. Gidaspow, D.T. Wasan, S. Saxena, Y.T. Shih, R.Gupta and A. Mukherjee, "Electrostatic Desulfurization of Coal in Fluidized Beds and Conveyers," AIChE Symposium(Series no.255), 83, 74-85. (1987). [16] D. H. Finseth, T. Newby and R. Elstrodt, "Dry Electrostatic Separation of Fine Coal," 5th Int. Conf. Proc. and Util. of High Sulfur Coals. Amsterdam: Elsevier Science Publishers. (1993). [17] I. I. Inculet, R.M. Quigley, M. A. Bergougnou, J. D. Brown, and D. K. Faurschou,. "Electrostatic beneficiation of hat creek coal in the fluidized state," Canadian Inst. Mining and Metallurgy Bulletin, vol. 73, p. 51-61. (1980) [18] V. Gente, F.L. Marca, F. Lucci and P. Massacci, "Electrical separation of plastics coming from special waste," Waste Manag23, 951958, 2003. [19] R. D. Pascoe and B. O. Connell, "Development of a method for separation of PVC and PET using flame treatment and flotation," Miner Eng, vol. 16, p. 12051212, 2003.

[20] I.I. Inculet, G.S.P. Castle and J.D. Brown, "Electrostatic separation of plastics for recycling," Part Sci Technol, p.p. 1691100, 1998. [21] Y. Wu, G.S.P. Castle and I.I. Inculet, "Particle size analysis in the study of induction charging of granular materials," J Electrost63, p.p. 189202, 2005. [22] A. Tilmatine, K. Medles, M. Younes, A. Bendaoud andL. Dascalescu, "Roll-type versus free-fall electrostatic separation of tribocharged plastic particles," IEEE/IAS Industry. ApplicationSociety. Volume 46, Issue: 4, pp: 1564 1569. 2010. [23] M .Bilici, L. Dascalescu, C. Dragan, O. Fati, A. Iuga and A. Samuila, "Tribocharging and electrostatic separation of mixed granular solids in fluidized bed devices," IEEE Trans. DEI, vol. 18, p. 1476-1483, 2011. [24] L. Calin, A. Mihalcioiu, A. Iuga and L. Dascalescu, "Fluidized bed device for plastic granules triboelectrification," Part. Sci .& Technol., vol. 25, p. 205-211, 2007. [25] L .Calin L. Caliap, V. Neamtu , R. Morar, A. Iuga, A. Samuila, and L. Dascalescu, , "Tribocharging of granular plastic mixtures in view of electrostatic separation," IEEE Trans. Ind. Appl., vol. 44, p. 10451051, 2008. [26] C. Dragan,O. Fati, M. Radu, L. Calin, A. Samuila, and L. Dascalescu, "Tribocharging of mixed granular plastics in a fluidized bed device," IEEE Trans. Ind. Appl., vol. 47, p. 1922 1928, 2011, [27] F.S. Ali, I.I. Inculet and A. Tedoldi, "Charging ofpolymer powder inside a metallic fluidized bed," J Electrost45, p.p. 199211, 1999. [28] A. Iuga, and al., "Tribocharging of plastics granulates in a fluidized bed device," J Electrost63, p.p. 937942, 2005. [29] R. McCown, and F.B. Gross," Medium velocity impacttriboelectrification experiments with JSC Mars-1 regolith stimulant, " J Electrostat64, p.p. 187193, 2006. [30] Y. Higashiyama, Y. Ujiie, and K. Asano, "Triboelectrification of plastic particles on a vibrating feeder laminated with a plastic film," J Electrostat42, p.p. 6368, 1997. [31] M.J. Pearse, and T.J. Hickey, "The separation of mixed plastics using a dry triboelectric technique," Resour Conserv Recy3, p.p. 179190, 1978. [32] D.K. Yanar and B.A. Kwetkus, "Electrostatic separation of polymer powders," J Electrostat35, p.p. 257266, 1995. [33] M. Miloudi, K. Medles, A. Tilmatine, M. Brahami andL .Dascalescu. "Optimisation of belt-type electrostatic separationof granular plastic mixtures tribocharged in a propeller-type device," Journal of Physics: Conference Series Volume 301 Number 1, 2011. 14 Apr2011 Electrostatics 2011 - 13th International Conferenceon Electrostatics in Bangor, UK at Bangor University.

[34] M. Miloudi, K. Medles, A. Tilmatine, M. Brahami and L. Dascalescu. "Modeling and Optimization of a Propeller-type Tribocharger for Granular Materials," J. Electrostat.,vol. 69, p.p. 631-637, 2011. application of triboelectric separation of plastics is relatively new. One of the earliest publications on this subject dates back to the early 1990s and originates from Canadian researchers that developed a triboelectric fluidizing bed (Fig. 13) for separation of different binary plastic mixtures results showed an effective triboelectric separation of acrylic, nylon PE or PVC, achiev-ing a purity of 95% or more Later, triboelectric charging of plastics by vibrating chute was also reported [53,54]. Moreover, Matsushita et al.[56] triboelectrically sorted mixed plastics by means of a rotating drum (Fig. 15), which was comprised of a cylinder with rotary blades, whose form was adapted to enhance mutual friction between plastic pieces. He reported that a mixture of two kinds of plastics was success-fully separated and the purity of products was not less than 90% [52] I.I. Inculet and G.S.P. Castle, Tribo-electrification of commercial plastic in air. Inst. Phys. Conf., Ser. No. 118: Section 4, paper presented at Electrostatics 91 (1991), pp. 217222. [53] T. Fujita, Y. Kamiya, N. Shimizu and T. Tanaka, Basic study of polymer particles separation using vibrating feeder and electrostatic high voltage generator. Proceedings of the Third International Symposium on East Asian Resources Recycling Technology(1995), pp. 155164. [54] M. Saeki, T. Inoue, M. Tukahara and H. Maehata, Vibro-electrostatic separation of plastics mixtures, Transactions of the Japan Society of Mechanical Engineers, 68(2002), 1420. (In Japanese with English abstract.) [56] Y. Matsushita, N. Mori and T. Sometani, Electrostatic separation of plastics by friction mixer with rotary drum blades,Electrical Engineering in Japan, 127(1999), 3340. Electrostatic separation appears as possible method on their separation. At this method electric field that is created between positive and negative electrode separates particles on the basisof charge size and polarity. By electrostatic separation of HDPE/PP mixture with particle size 11 mm was made possible from negative charged product to separate HDPE withrecovery 96.10% and from positive charged product to separate PP with recovery 97.52%.

Martin SISOL Frantika MICHALKOV Ivana KOZKOV Miroslava KOLESROV Triboelectric separation of PE and PP from municipal wastes ACTA FACULTATIS ECOLOGIAE, 16: Suppl. 1, 5-10 Zvolen (Slovakia), 2007 a three-component plastic mixture is purified by using the triboelectrostatic separation system, which employed a tribo-cyclone and a high voltage supply. Products of ABS, PS and PP with a grade of 92.1%, 84.9% and 90.0% respectively have been achieved with recoveries above 73.0% Gjergj Dodbiba, Atsushi Shibayama, Toshio Miyazaki and Toyohisa Fujita. Triboelectrostatic Separation of ABS, PS and PP Plastic Mixture. Materials Transactions, Vol. 44, No. 1 (2003) pp. 161 to 166 Rodbibaet al.[60] employed an air cyclone as a charging device to produce a higher frictional speed. He developed a triboelectric cyclone separa-tor (Fig. 16), which has been successfully tested in the laboratory for separating plastics. Considering his experimental results, the recovery of each collected product was higher than 75% while the purity was higher than 95%. G. Dodbiba, A. Shibayama, T. Miyazaki and T. Fujita, Electrostatic separation of the shredded plastic mixtures using a tribo-cyclone,Magnetic and Electrical Separation, 11(2001), 6392

Reactive blending
Blends of high-density polyethylene (HDPE) and polypropylene (PP) were prepared in different twinscrew extruders. Two additives, a peroxide initiator and a polymerizable monomer, were added to the polymeric feed components. A large influence on the physical properties, such as toughness and impact strength,. and on the morphology was observed. Reactive extrusion substantially improves mechanical properties: a three-fold increase of elongation at break and doubling of the impact strength. Variation of extruder settings also had a large influence on the product; the final properties were improved when the shear rate was raised, but sufficient residence time is necessary in reactive compatibilization. R. HEl3EM.A. J. VANTOL, andL. P. B. M. JANSSEN. In-Situ Reactive Blending of Polyethylene and Polypropylene in Co-Rotating and Counter-Rotating Extruders. POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 1999, Vol. 39, NO. 9 An attractive alternative is chemical modification of a blend by reactive extrusion (5) which can be a relatively cheap approach for improvement of the properties of a polymer blend (6). In a recent paper,

Hu (7) performed both grafting of PP with glycidyl methacrylate and blending with PI3T in a one-step extrusion process. The mechanical properties of the resulting blends were superior compared to the uncompatibilized blend. Fellahi et al. (8) have improved the stress at break and the impact strength of mixed plastics simply by processing it in the presence of a dialkyl peroxide. These improvements are most likely due to the formation of copolymers acting as compatibilizer by recombination of macroradicals. In addition, a reduction of the rheological mismatch for a blend containing low viscosity PE and high viscosity PP can enhance dispersive mixing. This is caused by the preferred reaction of these polymers with peroxide. The PE phase has a tendency for crosslinking (9). whereas PP with a peroxide mainly results in chain scission. Randall et al. (10) describe the preparation of impact modified PP blends by treating a reactor blend of PP and LLDPE with a peroxide. Various fragments will be present and recombine to form block or graft materials. This method increases the Gardner impact strength by 30%. Teh et al. (11) have concluded that one of the main problems in the modification of PE/PP blends with peroxide is the difficulty in controlling the degradation of the PP. These unwanted side reactions, such as chain scission and disproportionation, can be suppressed by addition of an unsaturated monomer (12). One function of these low molecular weight compounds is to promote the formation of copolymers (random, block or graft) resulting in improved compatibility. The monomer can stabilize the polyolefin macro radical sites (13) formed by the peroxide radicals, and create interchain block or graft copolymers by recombination. Another function of the monomer could be that of a vector fluid (14). This fluid is preferentially immiscible with both phases and carries the reactive ingredients to the interface. If the vector fluid is a polymerizable monomer, both polymers could obtain the Same grafts, resulting in stronger interactions at the interface (15). 5. M. Xanthos, Reactive Extrusion, Principles and Practice, Hanser Publishers, Munich (1992) 6. W. Wiedemann and H. Wohlfart-Laymann. Kunstst0ffe German plastics, 82, 10 (1992) 7.

The HyperSpectral Imaging (HSI) Technology

HyperSpectral Imaging [11] is a fast emerging technology that can be also profitably utilized for the analysis of particulate solid systems in terms of composition and spatial distribution. The technology can be used on-line and is cheap and powerful. HSI was originally developed for remote sensing applications [12] but has found application in such diverse fields as astronomy [13, 14], agriculture [15- 17], pharmaceuticals [18-20] and medicine [21-24]. In this last years several operative procedures and logics based on such a technology have been developed both at research and application level also in the recycling sector [25] for different waste materials [26, 27]. Hyperspectral cameras are able to deliver a wide spectrum of information on particulate solids streams. Investigated spectral responses are usually those belonging to VIS (400-700 nm) and VIS-NIR (400-1000 nm and 1000- 1700 nm) wavelengths ranges; they are usually correlated to particle composition. Together with spectral response other parameters are collected, as particle morphological and morphometrical attributes distribution, spatial and temporal fluctuations of the particle stream, etc. The development beyond the state-of-the-art will be to interpret the possibilities of HSI in determining the quality of feed and product streams in the recycling of post-consumer waste and translate the collected information into the parameters that are requested by the recycling operation, both in terms of control strategies set up and products quality assessment at the different stages of the processing. As an alternative to hyperspectral imaging, and to make operative comparisons, Dual Energy X-ray sensors are investigated as a means to detect chlorinated or bromated plastics as well as metallic impurities in the feed and separation products.
[12] A. F. H. Goetz, G. Vane, T. E. Solomon and B. N. Rock, Imaging spectrometry for earth remote sensing, Science, vol. 228, pp. 1147-1153, September 1985. *13+ E. Hege, D. OConnell, W. Johnson, S. Basty and E. Dereniak, Hyperspectral imaging for astronomy and space surveillance, Proceedings of the SPIE, 5159, 2003, pp. 380-391.

*14+ K. S. Wood, A. M. Gulian, G. G. Fritz and D. Van Vechten, A QVD detector for focal plane hyperspectral imaging. Astronomy. Bull. Am. Astronom. Soc., vol. 34, pp. 12-41, January 2002. [15] S. Monteiro, Y. Minekawa, Y. Kosugi, T. Akazawa and K. Oda, Prediction of sweetness and amino acid content in soybean crops from hyperspectral imagery, ISPRS J. Photogramm. Remote Sens., vol. 62, no. 1, pp. 2-12, January 2007. *16+ V. Smail, A. Fritz and D. Wetzel, Chemical imaging of intact seeds with NIR focal plane array assists plant breeding, Vib. Spectrosc., vol. 42, no. 2, pp. 215-221, February 2006. *17+ Y. Uno, S. Prasher, R. Lacroix, P. Goel, Y. Karimi and A. Viau, Artificial neural networks to predict corn yield from Compact Airborne Spectrographic Imager data. Comput. Electron. Agric., vol. 47, no. 2, pp. 149-161, January 2005. *18+ R. C. Lyon, D. S. Lester, E. N. Lewis, E. Lee, L. X. Yu and E. H. Jefferson, Near -infrared spectral imaging for quality assurance of pharmaceutical products: analysis of tablets to assess powder blend homogeneity, AAPS Pharm. Sci. Technol., vol. 3, no. 3, pp. 1-7, January 2002. *19+ O. Rodionova, L. Houmller, A. Pomerantsev, P. Geladi, J. Burger, V. Dorofeyev, NIR spectrom etry for counterfeit drug detection: a feasibility study, Anal. Chim. Acta, vol. 549, no. 1-2, pp. 151-158, January 2005. *20+ Y. Roggo, A. Edmond, P. Chalus and M. Ulmschneider, Infrared hyperspectral imaging for qualitative analysis of pharmaceutical solid forms, Anal. Chim. Acta, vol. 535, no. 1-2, pp. 79-87, January 2005. *21+ D. Ferris, R. Lawhead, E. Dickman, N. Holtzapple, J. Miller and S. Grogan, Multimodal hyperspectral imaging for the non invasive diagnosis of cervical neoplasia, J. Lower Genital Tract Dis., vol. 5, no. 2, pp. 65-72, January 2001. *22+ D. Kellicut, J. Weiswasser, S. Arora, J. Freeman, R. Lew and C. Shuman, Emerging technology: hyperspectral imaging, Perspectives Vascular Surg. Endovasc. Ther., vol. 16, no. 1, pp. 53-57, January 2004. *23+ G. Zheng, Y. Chen, X. Intes, B. Chance and J. D. Glickson, Contrast -enhanced near-infrared (NIR) optical imaging for subsurface cancer detection, J. Porphyrins Phthalocyanines, vol. 8, no. 9, pp. 1106-1117, December 2004. [24] A. A. Gowen, C. P. ODonnel, P. J. Cullen, G. Downey and J. M. Frias, Hyperspectral imaging an merging process analytical tool for food quality and safety control, Trends Food Sci. Technol., vol. 18, pp. 590-598, April 2007. [25] S. Serranti and G. Bonifazi, Solid waste materials characterization and recognition by hyperspectral imaging based logics, The 2nd Int. Symposium MBT 2007: Mechanical Biological Treatment and Automatic Sorting of Municipal Solid Waste, pp. 326-336, 2007. [26] G. Bonifazi and S. Serranti, Imaging spectroscopy based strategies for ceramic glass contaminants removal in glass recycling, Int. J. Waste Manage., vol. 26, pp. 627-639, June 2006. *27+ G. Bonifazi and S. Serranti Hyperspectral Imaging Based Techniques in Fluff Sorting. The 21st International Conference on Solid Waste Technology and Management: ICSWM 2006, pp. 740- 747. March 26-29, Philadelphia, PA, USA.

*28+ S. A. Sanaee and M. Bakker, Ultrasound for monitoring and quality inspection in MDS plastics recycling, ISWA-APESB, Lisbon, Portugal, 2009

HSI is a cost-effective emerging technology for the online assessment of particulate product streams. The aim of the project is to develop this technology into a monitoring tool for detecting foreign materials, such as rubber or wood in the input waste as well as in the polyolefin products. For the most ambitious applications, the sensors must be able to recognize materials other than Polyolefins at levels of 1% and less. HSI is based on the utilization of an integrated hardware and software architecture able to digitally capture and handle spectra, as an image sequence, as they results along a predefined alignment on a surface sample properly energized. According to the different wavelength of the source and the different spectral sensitivity of the device, different physicalchemical superficial characteristics of the sample can be investigated and analyzed. The hyperspectral imaging acquisition system adopted in this study is based on the utilization of a device: the ImSpectorTM V10E, belonging to the ImSpector series spectrometers, developed by SpecIm Oy, the system shown in (Fig. 5). The ImSpectorTM V10E operates in the spectral range between 400 nm and 1000 nm with a resolution of 2.8 nm. The acquired images are 780x580 pixel size, corresponding to 6.5x14.2 mm. The spectrograph is constituted by optics based on volume type holographic transmission grating. The grating is used in patented prism-grating-prism construction (PGP element) characterized by high diffraction efficiency, good spectral linearity and it is nearly free of geometrical aberrations due to the on-axis operation principle. A collimated light beam is dispersed at the PGP so that the central wavelength passes symmetrically through the grating and prisms and the short and longer wavelengths are dispersed up and down compared to central wavelength. This results in a minimum deviation from the ideal on-axis condition and minimizes geometrical aberrations both in spatial and spectral axis. The result of acquisition is a digital image where each column represents the discrete spectrum values of the

corresponding element of the sensitive linear array. Such an architecture allows, with a simple arrangement of the detection device (scan line perpendicular to the moving direction of the objects) to realize a full and continuous control. Line lighting, as energizing source with uniform spatial distribution, was thus used.

Fig. (5). Hyperspectral Imaging (HSI) based acquisition device to collect secondary plastic particles flow streams spectra

Chlorosulfonation Ultrasound process

A precise and on-line assessment of the composition of process streams is of the utmost importance for both the recycling and compounder industry in the transition to the recycling of post-consumer wastes. The former needs it to monitor the separation process. The latter demands it for the most accurate (and fast) composition assessment to calibrate the extruders (equipments) and to fulfill customers requirements as well. Therefore fast on-line assessment is a key point to increase the value of secondary Polyolefins. The state-of-the-art analysis of PP or PE concentrates in terms of the concentration of the other Polyolefin as well as non-polyolefin contaminants is by means of hand-sorting and thermal DSC analysis of samples in the laboratory. Other methods are CRYSTAF, Infra-red spectroscopy [9] and TREF [10]. Neither of these methods is suitable and accurate for the required on-line quality assessment and so sensor technology must be

developed that is able to quantify the concentration of contaminants and particle size distribution in each of the products. Ultrasound has proved to be a useful tool in the quality assessment of materials and 4-D imaging of interfaces between solids and liquids. The technology is extremely advanced in geology, navigation and in medical fields. Applications also concern with leak detection, tightness testing, and predictive maintenance, etc. Ultrasound imaging technology has developed very fast into a tool with a high resolution (about 1 mm pixel width) and a short capture time (less than 0.1 second per frame). The special feature of the technology is that the image clearly shows internal interfaces between solids and liquids with a slightly different speed of sound. Therefore, the technique has the potential to measure both the spatial distribution of solids as well as their shape and material/interface properties. Ultrasound imaging technology uses the pulse-echo technique as in navigation (SONAR) and other applications. The ultrasound arrays transmit ultrasonic sound pulses (also known as sound waves), into the part of interest inside the imaged volume, which can range from industrial parts to organs of human bodies. As soon as the sound waves hit the boundary between materials with different phases they are reflected back to the probe/receiver. These ultrasonic echoes and the time intervals for them to be reflected are recorded. From the time of each echos return and the known speed of sound, the distances of the different interfaces from the probe/receiver are determined. Then data are processed by inversion algorithms and the distances as well as the intensities of these echoes are displayed, resulting in a two, three or four dimensional image (movie). Best results are obtained in applications where the various materials have a comparable speed of sound, to facilitate a balance of transmission and reflection along with the generation of echoes. The development beyond the state-of-the-art in ultrasound technology in this project is to design an array and solve the inverse problem of sound travelling through the suspension to create 4D images of the suspension of particles in the MDS channel for the present application. The aim is to interpret the

echo into the spatial distribution and brightness of particles. These data can be related to the apparent density, internal speed of sound and surface texture of the particles and therefore to the quality of the feed and the separation. [10] N. Samoth, S. Tantayanon, V. Tangpasuthadol and K. Phalakornkul, Polyethylene Fractionation by
Modified Temperature Rising Elution Fractionation Technique. Proceeding of the 8th Polymers for Advanced Technologies International Symposium. Budapest, Hungary, 2005.

*11+ G. Bonifazi and S. Serranti, Hyperspectral Imaging Based Techniques in Particles and Particulate So lids Systems Characterization. The 5th International Conference for Conveying and Handling of Particulate Solids : CHoPS-05, Sorrento, Italy, 2006.

Despite the potential accuracy of MDS, some contamination of the products is unavoidable due to the natural overlapping of density ranges of the different materials. The extent to which this problem occurs depends on the composition of the actual feed material and so it cannot be solved in the design stage. For this reason, a precise and on-line assessment of the composition of process streams will be developed on the basis of ultrasound to allow making the best possible product from a given feedstock. The ultrasound imaging technology needed is beyond the state-of-the-art and aims to interpret the echo from particles suspended in the magnetic fluid into the spatial distribution and brightness of materials, such that differences between the various polyolefins and contaminants can be recognized and through the differences of their spatial distribution can be translated into product qualities. The same ultrasound technology is also crucial to detect obstructions of the flow or sub-optimal splitter settings. To date the possibility to adapt off-the-shelf medical imaging technology was investigated with an eye towards the real-time requirements for industrial MDS monitoring. It is shown that a medical system can be adapted for monitoring the flowing plastics for particle speeds up to 30 cm/s. The imaging quality can be quite good under optimum viewing angle conditions, and may then also allow for quantitative through-put analysis (Fig. 4). Moreover the potential of ultrasound for materials characterization from

inside the magnetic fluid was investigated through research on wave generation and propagation in wave attenuating media through experiments and 3D acoustic modelling. Using a calibrated measurement setup it has been shown that different polyolefin groups are acoustically distinctive, which is the primary condition for ultrasound quality inspection.

Fig. (4). Example of the potentialities offered by the application of medical ultrasound imaging technology applied to plastics particles identification inside a fluid.

Partial oxidation Thermal treatment Mechanical treatment Mechanical milling

Mechanical milling is the process whereby solid powders are generated, reduced in size and mixed together to produce alloys at the molecular level. Application of this technique has lagged far behind initial efforts by Shaw and Pan[1], followed by studies by Klementina and Torkelson[2], Smith et al.[35] and Cavalieri et al.[6]. Various methods have been used by these researchers to pulverize the mixed

polymer. Ball milling was the most commonly used pulverizing technique, although Klementina used a twin-screw extruder at cryogenic temperatures. Good improvements in the physical properties of the resultant polymer have been reported in all the above-mentioned processes. [1] J.K. Shaw, J. Pan, Microstructural Science 19 (1992) 659. [2] K. Klementina, J.M. Torkelson, Solid-state shear pulverization of plastics: a green recycling process, Polymer-Plastic Technology Engineering 38 (3) (1999) 445457. [3] A.P. Smith, H. Ade, K.C. Koch, S.D. Smith, R.J. Spontak, Addition of block copolymer to polymer blends produced by cryogenic mechanical alloying, Macromolecules 33 (2000) 11631172. [4] A.P. Smith, H. Ade, K.C. Koch, S.D. Smith, R.J. Spontak, Solid-state blending of polymers by cryogenic mechanical alloying, Material Research Society Symposium 629 (2000) 691696. [5] A.P. Smith, H. Ade, C.C. Koch, R.J. Spontak, Cryogenic mechanical alloying as an alternative strategy for the recycling of tires, Polymer 42 (9) (2000) 44534457. [6] F. Cavalieri, F. Padella, S. Bourbonneux, C. Romanelli, Mechano-chemical recycling of mixed plastic waste, retrieved from http://modest.unipa.it/conferences/2000/html/symp9/ P9Th01.pdf, 2000.

Cryogenic ball milling

Cryogenic ball milling is a mechanical alloying process where the high energy impact conditions in a ball mill pulverizes the mixed plastics into a powder. Smith et al.[3 5]used SPEX 8000 mixer/mills manufactured by SPEX Certiprep Sample Preparation Incorporated for the mech-anical alloying. This is a high energy shaker mill capable of mixing up to 10 ml of material per batch. Milling was performed to incorporate two rubbery polymers, polyiso-prene (PI) and polyethylene-alt-propylene (PEP) into a commodity thermoplastic, polymethyl methacrylate (PMMA), which are known to be immiscible, and found that blend was formed with acceptable mechanical proper-ties[3,8]. It took nearly 10 h to pulverize the mixed polymer to a size of 2mm. The process was carried out at cryogenic temperatures by means of liquid nitrogen[3,5]. Impact tests on PI/MI/PMMA 22/6/72 blends were reported to show an improvement in the impact strength. [7] A.P. Smith, Solid-State Blending and Compatibilization of Polymers by Cryogenic Mechanical Alloying, PhD Thesis, North Carolina State University, 1999.

[8] A.P. Smith, J.S. Richard, H. Ade, S.D. Smith, C.C. Koch, High-energy cryogenic blending and compatibilizing of immiscible polymers, Advanced Materials 11 (15) (1999) 12771281

Carbon dioxide assisted ball milling

Cavalieri performed mechanical alloying to reprocess mixed polymer waste of unspecified composition by means of a high-energy ball milling process in a liquid carbon dioxide medium. The process was found effective to pulverize polymer particles or shredded polymer films, in a very short-milling time, promoting a substantial size reduction and mechano-chemical modification on the material, resulting in good mechanical properties of the blend. The process claims to compatibilize polymeric mixtures, regardless of the chemical composition[9]. This was reported effective to co-pulverize polymer particles in a very short-milling time (10 min compared to 10 h in the previous case), while compatibilizing the immiscible polymers involved in the mixed polymer waste [10]. Punch strength was reported to improve with milling. In the case of CO2assisted ball milling, CO2is claimed to act as catalyst, which enhances the mechanochemical effects promoted by the milling action. The energy transfer from the milling device to milled powder occurs during the hit between balls and the vial wall. The CO2trapped between the ball and the vial wall absorbs the energy of the hit and produces micro-explosive evaporation of liquid CO2that disrupts the solid material[9]. Hence, the material is pulverized much quicker compared to the one using liquid nitrogen. [9] F. Cavalieri, F. Padella, High-energy mechanical alloying of thermoplastic polymers in carbon dioxide, Polymer 43 (4) (2002) 11551161. [10] F. Cavalieri, F. Padella, Development of composite materials by mechano-chemical treatment of post-consumer polymer waste, Waste Management 22 (13) (2002) 913916

Cryogenic extrusion
Cryogenic extrusion refers to the mechanical alloying process using an extruder at cryogenic temperatures. Solid-state shear pulverization (S 3 P) ([1113]) and the solid-state shear extrusion (S 3 E)[4,15]are similar cryogenic extrusion processes used to recycle single or commingled post- or pre-

consumer polymeric waste. The S 3 P-made powders are reported to be melt-processable by all conventional plastic fabrication techniques and possess a higher tensile strength and modulus compared to the melt-extruded polymer. S 3 P has been used to recycle a wide range of post- and pre-consumer plastics (HDPE, LDPE, PP, PS, PVC, PET), and their blends, into value added materials. [11] K. Klementina, S. Carr, Solid-state Shear Pulverization: A New Polymer Processing and Powder Technology, Technomic Publishing Company, Lancaster, PA, 2001. [12] K. Klementina, E. Riddick, Recycling of post-consumer agricultural film via solid-state shear pulverization, Global Plastics Environment Conference (GPEC 2002) of the Society of Plastics Engineers, February 1314, Detroit, Michigan, 2002. [13] K. Klementina, E. Stephen, A new environmentally friendly recycling technology: solid-state shear pulverization (S3P), retrieved from http://dtwws1.vub.ac.be/chis2/ ISFR%202002%20CD/paper/A47.doc, 2002. [14] F. Shutov, G. Ivanov, H. Arastoopour, Solid-state shear extrusion pulverization, US Patents 5,397,065, 1995. [15] H. Arastoopour, Single-screw extruder for solid-state shear extrusion pulverization and method, US Patents, 5,397,065, 1998

Solid state shear pulverization

Solid-state shear pulverization (SSSPTM/ is a novel, environmentally benign, and continuous processing technique that applies high shear and compressive forces to polymeric materials, resulting in fragmentation and fusion steps in the solid state.1 One key advantage of SSSP over conventional meltprocessing techniquese.g., twin screw-extrusion (TSE)is that SSSP overcomes physical hindrances such as thermodynamic barrier and viscosity mismatch to synthesize materials with desired structures (morphologies). Thus far, SSSP has been suc-cessfully employed for mechanochemical modification of polymers, 25 compatibilization of polymer blends, 3, 4, 68 exfoliation and dispersion of fillers in polymer nanocomposites,912 solid-state compound-ing of colored powders, 13 and recycling of commodity plastics. 6, 1416 Despite its proven success in producing novel polymeric mat-erials with enhanced properties, little has been published about the detailed mechanism of the process 1. K. Khait and S. H. Carr, Solid-State Shear Pulverization: A New Polymer Process-ing and Powder Technology, Technomic Publ. Co., Lancaster, 2001. 2. C. Pierre, A. Flores, K. Wakabayashi, and J. M. Torkelson, Solid-state shear pulver-ization: an alternative to nucleating agents for some semi-crystalline polymers, SPE ANTEC 66, p. 2082, 2008.

3. A. H. Lebovitz, K. Khait, and J. M. Torkelson, Sub-micron dispersed-phase particle size in polymer blends: overcoming the Taylor limit via solid-state shear pulverization, Polymer 44 (1), pp. 199206, 2003. 4. Y. Tao, J. Kim, and J. M. Torkelson, Achievement of quasi-nano structured polymer blends by solidstate shear pulverization and compatibilization by gradient copolymer addition, Polymer 47 (19), pp. 67736781, 2006. doi:10.1016/j.polymer.2006.07.041 5. M. Diop and J. M. Torkelson, Ester functionalization and structural modification of polypropylene via solid-state shear pulverization, SPE ANTEC, 2012. accepted 6. K. Khait and J. M. Torkelson, Solid-state shear pulverization of plastics: a green recycling process, Polym.-Plast. Technol. Eng. 38 (3), pp. 445457, 1999. doi:10.1080/03602559909351592 7. M. Ganglani, J. M. Torkelson, S. H. Carr, and K. Khait, Trace levels of mechanochem-ical effects in pulverized polyolefins, J. Appl. Polym. Sci. 80 (4), pp. 671679, 2001. 8. K. Wakabayashi, Y. Tao, A. H. Lebovitz, and J. M. Torkelson, Solid state shear pulver-ization as a realworld process for polymer blends and nanocomposites, SPE ANTEC 65, p. 1528, 2007. 9. K. Wakabayashi, C. Pierre, D. A. Dikin, R. S. Ruoff, T. Ramanathan, L. C. Brinson, and J. M. Torkelson, Polymer-graphite nanocomposites: effective dispersion and ma-jor property enhancement via solidstate shear pulverization, Macromolecules 41 (6), pp. 19051908, 2008. doi:10.1021/ma071687b 10. J. Masuda and J. M. Torkelson, Dispersion and major property enhancements in polymer/multiwall carbon nanotube nanocomposites via solid-state shear pulver-ization followed by melt mixing, Macromolecules 41 (16), pp. 59745977, 2008. doi:10.1021/ma801321j 11. K. Wakabayashi, P. J. Brunner, J. Masuda, S. A. Hewlett, and J. M. Torkelson, Polypropylene-graphite nanocomposites made by solid-state shear pulverization: effects of significantly exfoliated, unmodified graphite content on physical, mechanical, and electrical properties, Polymer 51 (23), pp. 55255531, 2010. doi:10.1016/j.polymer.2010.09.007 12. J. Masuda and J. M. Torkelson, Polym. Eng. Sci, to be submitted. 13. P. Brunner and J. M. Torkelson, Overcoming technological issues associated with color additives in polymers via solid-state shear pulverization, SPE ANTEC, in press. 14. K. Khait and S. H. Carr, Value-added materials made from recycled plastics, SPE ANTEC 55, p. 3086, 1997. 15. K. Khait and S. H. Carr, Mixed polyolefin powders recycled via solid-state shear pul-verization process, SPE ANTEC 56, p. 2533, 1998. 16. K. Khait and S. H. Carr, Toughened recycled polypropylene: blends produced via the solid-state shear pulverization process, SPE ANTEC 56, p. 2939, 1998.

Surface Plasmon Resonance

Polymer wise processing

Concluding remarks Future prospects

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KMPG. The future of the chemical industry. 2010. Wurpel G., V.d.A.J., Pors J., Ten Wolde., Plastics do not belong in the ocean. Towards a roadmap for a clean North Sea. IMSA Amsterdam, 2011. Yoshida H, S.K., Aizawa H. R, strategies for the establishment of an international sound materialcycle society. Journal of Material Cycles and Waste Management, 2007. 9(2). Larsen AW, M.H., Mller J, Christensen TH. , Waste collection systems for recyclables: an environmental and economic assessment for the municipality of Aarhus (Denmark). Waste Management 2010. 30(5). Brandrup J, B.M., Michaeli W, Menges G. Munich, New York: ; , Recycling and recovery of plastics., C.H. Verlag, Editor 1996. p. 893. Lucas, N.B., C.; Belloy, C.; Queneudec, M.; Silvestre, F.; Nava-Saucedo, J.E, Polymer biodegradation: mechanisms and estimation techniques. Chemosphere, 2008. 73: p. 429-442. Cho, J.W.W., K.S.; Chun B.C.; Park, J.S, Ultraviolet selective and mechanical properties of polyethylene mulching films. Eur. Polym. J, 2001. 37: p. 1227-1232. Willett, J.L., Mechanical properties of LDPE/granular starch composites. J. Appl. Polym. Sci, 1994. 54: p. 1685-1695. Lawton, J.T., Effect of starch type on the properties of starch containing films. Carbohydr. Polym, 1996. 29: p. 203-208. Jaserg, B.S., C.; Nelsen, T.; Doane, W, Mixing polyethylene-poly(ethylene-co-acrylic acid) copolymer starch formulations for blown films. J. Polym. Mat., 1992. 9: p. 153-162. Briassoulis, D., Mechanical behaviour of biodegradable agricultural films under real field conditions. Polym. Deg. Stab, 2006. 91: p. 1256-1272. Tighzert, I.V.a.L., Review Biodegradable Polymers. Materials, 2009. 2: p. 307-344.

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KMPG. The future of the chemical industry. 2010. Wurpel G., V.d.A.J., Pors J., Ten Wolde., Plastics do not belong in the ocean. Towards a roadmap for a clean North Sea. IMSA Amsterdam, 2011. Yoshida H, S.K., Aizawa H. R, strategies for the establishment of an international sound materialcycle society. Journal of Material Cycles and Waste Management, 2007. 9(2). Larsen AW, M.H., Mller J, Christensen TH. , Waste collection systems for recyclables: an environmental and economic assessment for the municipality of Aarhus (Denmark). Waste Management 2010. 30(5). Brandrup J, B.M., Michaeli W, Menges G. Munich, New York: ; , Recycling and recovery of plastics., C.H. Verlag, Editor 1996. p. 893. Lucas, N.B., C.; Belloy, C.; Queneudec, M.; Silvestre, F.; Nava-Saucedo, J.E, Polymer biodegradation: mechanisms and estimation techniques. Chemosphere, 2008. 73: p. 429-442. Cho, J.W.W., K.S.; Chun B.C.; Park, J.S, Ultraviolet selective and mechanical properties of polyethylene mulching films. Eur. Polym. J, 2001. 37: p. 1227-1232. Willett, J.L., Mechanical properties of LDPE/granular starch composites. J. Appl. Polym. Sci, 1994. 54: p. 1685-1695. Lawton, J.T., Effect of starch type on the properties of starch containing films. Carbohydr. Polym, 1996. 29: p. 203-208. Jaserg, B.S., C.; Nelsen, T.; Doane, W, Mixing polyethylene-poly(ethylene-co-acrylic acid) copolymer starch formulations for blown films. J. Polym. Mat., 1992. 9: p. 153-162. Briassoulis, D., Mechanical behaviour of biodegradable agricultural films under real field conditions. Polym. Deg. Stab, 2006. 91: p. 1256-1272. Tighzert, I.V.a.L., Review Biodegradable Polymers. Materials, 2009. 2: p. 307-344. Slabosz, T. Waste and Sustainability - Biodegradable and Non-Biodegradable Materials. 2009.

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KMPG. The future of the chemical industry. 2010. Wurpel G., V.d.A.J., Pors J., Ten Wolde., Plastics do not belong in the ocean. Towards a roadmap for a clean North Sea. IMSA Amsterdam, 2011. Yoshida H, S.K., Aizawa H. R, strategies for the establishment of an international sound materialcycle society. Journal of Material Cycles and Waste Management, 2007. 9(2). Larsen AW, M.H., Mller J, Christensen TH. , Waste collection systems for recyclables: an environmental and economic assessment for the municipality of Aarhus (Denmark). Waste Management 2010. 30(5). Brandrup J, B.M., Michaeli W, Menges G. Munich, New York: ; , Recycling and recovery of plastics., C.H. Verlag, Editor 1996. p. 893. Lucas, N.B., C.; Belloy, C.; Queneudec, M.; Silvestre, F.; Nava-Saucedo, J.E, Polymer biodegradation: mechanisms and estimation techniques. Chemosphere, 2008. 73: p. 429-442. Cho, J.W.W., K.S.; Chun B.C.; Park, J.S, Ultraviolet selective and mechanical properties of polyethylene mulching films. Eur. Polym. J, 2001. 37: p. 1227-1232. Willett, J.L., Mechanical properties of LDPE/granular starch composites. J. Appl. Polym. Sci, 1994. 54: p. 1685-1695. Lawton, J.T., Effect of starch type on the properties of starch containing films. Carbohydr. Polym, 1996. 29: p. 203-208. Jaserg, B.S., C.; Nelsen, T.; Doane, W, Mixing polyethylene-poly(ethylene-co-acrylic acid) copolymer starch formulations for blown films. J. Polym. Mat., 1992. 9: p. 153-162. Briassoulis, D., Mechanical behaviour of biodegradable agricultural films under real field conditions. Polym. Deg. Stab, 2006. 91: p. 1256-1272. Tighzert, I.V.a.L., Review Biodegradable Polymers. Materials, 2009. 2: p. 307-344. Slabosz, T. Waste and Sustainability - Biodegradable and Non-Biodegradable Materials. 2009. Metzger P, L.C.B.b., A rich source for hydrocarbons and related ether lipids. Appl Microbiol Biotechnol, 2005. 66: p. 486-496. Frost JW, D.K., Biocatalytic syntheses of aromatics from D-Glucose - renewable microbial sources of aromatic compounds. Annu Rev Microbiol, 1995. 49: p. 557-579. Scheeline HW, I.R., Ethylene to ethanol, in InProcess Economics Program Reports and Reviews1980, SRI Consulting: Houston. Yamada H, K.M., Nitrile hydratase and its application to industrial production of acrylamide. Biosci Bitechnol Biochem, 1996. 60: p. 1391-1400.

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Galli P, V.G., Technology: Driving force behind innovation and growth of polyolefins. Prog Polym Sci, 2001. 26(8). Scott, G., Green polymers. Polym. Degrad. Stab, 2000. 68(1): p. 1-7. Wiles, G.S.a.D.M., Programmed-Life Plastics from Polyolefins: A New Look at Sustainability. Biomacromolecules, 2001. 2(3). Scott, G., Atmospheric Oxidation and Antioxidants, Elsevier, Editor 1993: New York. p. Chapters 3, 5, 8, and 9. Omichi, H., Degradation and Stabilisation of Polyolefins, N.S. Allen, Editor 1983, Applied Science Publishers: London. p. Chapter 4. Scott, G., Biodegradable Plastics and Polymers, Y. Doi, Fukuda, K., Editor 1994, Elsevier Science BV: Amsterdam. p. 79-91. Wiles, D.M., Tung, J. F., Cermak, B. E., Gho, J. G., Hare, C. W. J. . in Biodegradable Plastics. 2000. Frankfurt: European Plastics News. Scott, G., Polymers and the EnVironment, 1999, Royal Society of Chemistry: Cambridge. p. Chapter 5. Sanaee., M.C.M.B.a.S.A., Capabilities of Ultrasound for Monitoring and Quantitative Analysis of Polyolefin Waste Particles in Magnetic Density Separation (MDS). The Open Waste Management Journal, 2010. 3. Development and Forecast of China Polyolefin Industry, in CPIC2013, CNCIC Consulting: Singapore. p. 10. ACHILIAS, D.S., ANTONAKOU, ., ROUPAKIAS, C., MEGALOKONOMOS, P., LAPPAS, A. , RECYCLING TECHNIQUES OF POLYOLEFINS FROM PLASTIC WASTES. GLOBAL NEST JOURNAL, 2008. 10(1). Jakubowicz, I., Evaluation of degradability of biodegradable polyethylene (PE). Polym. Deg. Stab, 2003. 80: p. 39-43. Cornell, D.D., Plastics, Rubber, and Paper Recycling-A Pragmatic Approach. American Chemical Society, Washington,, 1995. ; Available from: http://www.plasticseurope.org. .

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KMPG. The future of the chemical industry. 2010. Wurpel G., V.d.A.J., Pors J., Ten Wolde., Plastics do not belong in the ocean. Towards a roadmap for a clean North Sea. IMSA Amsterdam, 2011. Yoshida H, S.K., Aizawa H. R, strategies for the establishment of an international sound materialcycle society. Journal of Material Cycles and Waste Management, 2007. 9(2). Larsen AW, M.H., Mller J, Christensen TH. , Waste collection systems for recyclables: an environmental and economic assessment for the municipality of Aarhus (Denmark). Waste Management 2010. 30(5). Brandrup J, B.M., Michaeli W, Menges G. Munich, New York: ; , Recycling and recovery of plastics., C.H. Verlag, Editor 1996. p. 893. Lucas, N.B., C.; Belloy, C.; Queneudec, M.; Silvestre, F.; Nava-Saucedo, J.E, Polymer biodegradation: mechanisms and estimation techniques. Chemosphere, 2008. 73: p. 429-442. Cho, J.W.W., K.S.; Chun B.C.; Park, J.S, Ultraviolet selective and mechanical properties of polyethylene mulching films. Eur. Polym. J, 2001. 37: p. 1227-1232. Willett, J.L., Mechanical properties of LDPE/granular starch composites. J. Appl. Polym. Sci, 1994. 54: p. 1685-1695.

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