Process efficiency in polymer extrusion: Correlation between the energy demand and melt thermal stability

Thermal stability is of major importance in polymer extrusion, where product quality is dependent upon the level of melt homogeneity achieved by the extruder screw. Extrusion is an energy intensive process and optimisation of process energy usage while maintaining melt stability is necessary in order to produce good quality product at low unit cost. Optimisation of process energy usage is timely as world energy prices have increased rapidly over the last few years. In the first part of this study, a general discussion was made on the efficiency of an extruder. Then, an attempt was made to explore correlations between melt thermal stability and energy demand in polymer extrusion under different process settings and screw geometries. A commodity grade of polystyrene was extruded using a highly instrumented single screw extruder, equipped with energy consumption and melt temperature field measurement. Moreover, the melt viscosity of the experimental material was observed by using an off-line rheometer. Results showed that specific energy demand of the extruder (i.e. energy for processing of unit mass of polymer) decreased with increasing throughput whilst fluctuation in energy demand also reduced. However, the relationship between melt temperature and extruder throughput was found to be complex, with temperature varying with radial position across the melt flow. Moreover, the melt thermal stability deteriorated as throughput was increased, meaning that a greater efficiency was achieved at the detriment of melt consistency. Extruder screw design also had a significant effect on the relationship between energy consumption and melt consistency. Overall, the relationship between the process energy demand and thermal stability seemed to be negatively correlated and also it was shown to be highly complex in nature. Moreover, the level of process understanding achieved here can help to inform selection of equipment and setting of operating conditions to optimise both energy and thermal efficiencies in parallel. 

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)(2)(PPh3)(2) as well as the commercially important metal organic frameworks (MOFs) Cu-3(BTC)(2) (HKUST-1), Zn(2-methylimidazolate)(2) (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h(-1) rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3-4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h(-1). The space time yields (STYs) for these methods of up to 144 x 10(3) kg per m(3) per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.

Viscosity Control for Extrusion Processes Using Recycled Polymers

The aim of this paper is to develop a new extruder control system for recycled materials which has ability to automatically maintain constant a polymer melt viscosity of mixed recycled polymers during extrusion, regardless of variations in the Melt Flow Index (MFI) of recycled mixed grade high density polyethylene (HDPE) feedstock. A closed-loop controller is developed to automatically regulate screw speed and barrel temperature profile to achieve constant viscosity and enable consistent processing of variable grade recycled HDPE materials. The experimental results of real time viscosity measurement and control using a 38mm single screw extruder with different recycled HDPEs with widely different MFIs are reported in this work

Characterization and structure–property relationship of melt-mixed high density polyethylene/multi-walled carbon nanotube composites under extensional deformation

Melt-mixed high density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites with 1–10 wt% MWCNTs were prepared by twin screw extrusion and compression moulded into sheet form. The compression moulded nanocomposites exhibit a 112% increase in modulus at a MWCNT loading of 4 wt%, and a low electrical percolation threshold of 1.9 wt%. Subsequently, uniaxial, sequential (seq-) biaxial and simultaneous (sim-) biaxial stretching of the virgin HDPE and nanocomposite sheets was conducted at different strain rates and stretching temperatures to investigate the processability of HDPE with the addition of nanotubes and the influence of deformation on the structure and final properties of nanocomposites. The results show that the processability of HDPE is improved under all the uniaxial and biaxial deformation conditions due to a strengthened strain hardening behaviour with the addition of MWCNTs. Extensional deformation is observed to disentangle nanotube agglomerates and the disentanglement degree is shown to depend on the stretching mode, strain rate and stretching temperatures applied. The disentanglement effectiveness is: uniaxial stretching < sim-biaxial stretching < seq-biaxial stretching, under the same deformation parameters. In sim-biaxial stretching, reducing the strain rate and stretching temperature can lead to more nanotube agglomerate breakup. Enhanced nanotube agglomerate disentanglement exhibits a positive effect on the mechanical properties and a negative effect on the electrical properties of the deformed nanocomposites. The ultimate stress of the composite containing 4 wt% MWCNTs increased by ∼492% after seq-biaxial stretching, while the resistivity increased by ∼1012 Ω cm.

Effect of cooling rate on the properties of high density polyethylene/multi-walled carbon nanotube composites

High density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by melt mixing using twin-screw extrusion. The extruded pellets were compression moulded at 200°C for 5min followed by cooling at different cooling rates (20°C/min and 300°C/min respectively) to produce sheets for characterization. Scanning electron microscopy (SEM) shows that the MWCNTs are uniformly dispersed in the HDPE. At 4 wt% addition of MWCNTs composite modulus increased by over 110% compared with the unfilled HDPE (regardless of the cooling rate). The yield strength of both unfilled and filled HDPE decreased after rapid cooling by about 10% due to a lower crystallinity and imperfect crystallites. The electrical percolation threshold of composites, irrespective of the cooling rate, is between a MWCNT concentration of 1∼2 wt%. Interestingly, the electrical resistivity of the rapidly cooled composite with 2 wt% MWCNTs is lower than that of the slowly cooled composites with the same MWCNT loading. This may be due to the lower crystallinity and smaller crystallites facilitating the formation of conductive pathways. This result may have significant implications for both process control and the tailoring of electrical conductivity in the manufacture of conductive HDPE/MWCNT nanocomposites.

Silane Grafting of Polyethylenes

Reactive extrusion is an attractive means of polymer processing since the shaping and reaction take place in a single operation. In this paper we report the silane grafting of polyethylenes in a single screw extruder. The optimum conditions for silane grafting, viz. temperature, shear rate, silane and DCP concentrations, were determined on a torque rheometer and then actual extrusion was performed using these conditions. The study shows that an optimum low level of grafting/ crosslinking can be introduced into polyethylene during its extrusion for better mechanical behavior and=or thermal stability without affecting the processability.

Modification of Polyethylenes by Reactive Extrusion

The main aim of the study was to optimise the reactive extrusion conditions in the conventional modification processes of polyethylenes in a single screw extruder.The optimum conditions for peroxide crosslinking of low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and their blend were determined in a torque rheometer. The actual reactive extrusion was performed in a laboratory single screw extruder using the optimum parameters. The influence of the coagent, triaUyl cyanurate (TAC), on the cross linking of low density polyethylene in the presence of peroxide was also investigated. The peroxide crosslinking was found to improve the mechanical properties and the thermal stability of the polyethylenes. The efficiency of crosslinking was found to be improved by the addition of coagent such as TAC.The optimum conditions for silane grafting viz temperature, shear rate, silane and DCP concentrations were determined on a torque rheometer in the case of LDPE, LLDPE and their blend. Silane grafting of LDPE in the presence of peroxide was performed with and without addition of water. Compounding of such mixtures in the melt at high temperatures caused decomposition of the peroxide and grafting of alkoxy silyl groups to the polyethylene chains.The optimum parameters for maleic anhydride modification of LDPE, LLDPE and their blend were determined. The grafting reaction was confinned by FTIR spectroscopy. Modification of polyethylenes with maleic anhydride in the presence of dicumyl peroxide was found to be useful in improving mechanical properties. The improvement was found to be mainly due to the grafting of carboxyl group and formation of crosslinks between the chains. The cross linking initiated improvements indicate extended property profiles and new application fields for polyethylenes.On the whole the study shows that the optimum conditions for modifying polyethylenes can be determined on a torque rheometer and actual modification can be performed in a single screw extruder by employing the optimum parameters for improved mechanical! thermal behaviour without seriously affecting their processing behaviour.

Effect of Feeding Rate in Polymer Extrusion ”

Starve feeding of single screw extruder was described as an important means of improving the performance characteristics of the extruder. In addition to such improvement with versatility, the starve feeding technique also may affect the mechanical properties of the extrudate since the heat transfer an(l mixing characteristics in the starve fed and Hood fed extruders are not the same. Since the material is more loosely packed in the channels of the starve fed extruder, there may be greater bed mobility and uniformity. Further, the. thermal an(l shear induced degradation are also less since possibilities of developing local high temperatures are less compared to a densely compacted extruder bed. This study has been undertaken mainly to explore the effect of feeding rate on the mechanical properties of rubber and plastic extrudates since the effect of feeding rate has not been analysed from this angle so far.

Effects of Extrusion on the Emulsifying Properties of Rumen and Soy Protein

Defatted rumen protein and soy protein concentrate were extruded in a 15.5:1 L/D single-screw extruder at the optimum conditions for their expansion (150A degrees C and 35% moisture, and 130A degrees C and 35% moisture, respectively). Emulsions were produced with these proteins and studied by rheology and time domain low-resolution (1)H nuclear magnetic resonance (TD-NMR). Extrusion increased storage modulus of rumen protein emulsions. The opposite was observed for soy protein. Mechanical relaxation showed the existence of three relaxing components in the emulsions whose relative contributions were changed by extrusion. Likewise, spin-spin relaxation time constants (T (2)) measured by TD-NMR also showed three major distinct populations of protons in respect to their mobility that were also altered by extrusion. Extrusion increased surface hydrophobicity of both rumen and soy protein. Solubility of rumen protein increased with extrusion whereas soy protein had its solubility decreased after processing. Extrusion promoted molecular reorganization of protein, increasing its superficial hydrophobicity, affecting its interfacial properties and improving its emulsifying behavior. The results show that extrusion can promote the use of rumen, a by-product waste from the meat industry, in human nutrition by replacing soy protein in food emulsions.

Soda-Treated Sisal/Polypropylene Composites

Treated sisal fibers were used as reinforcement of polypropylene (PP) composites, with maleic anhydride-grafted PP (MAPP) as coupling agent. The composites were made by melting processing of PP with the fiber in a heated roller followed by multiple extrusions in a single-screw extruder. Injection molded specimens were produced for the characterization of the material. In order to improve the adhesion between fiber and matrix and to eliminate odorous substances, sisal fibers were treated with boiling water and with NaOH solutions at 3 and 10 wt.%. The mechanical properties of the composites were assessed by tensile, bend and impact tests. Additionally, the morphology of the composites and the adhesion at he fiber-matrix interface were analyzed by SEM. The fiber treatment led to very light and odorless materials, with yields of 95, 74 and 62 wt.% for treatments with hot water, 3 and 10 wt.% soda solution respectively. Fiber treatment caused an appreciable change in fiber characteristics, yet the mechanical properties under tensile and flexural tests were not influenced by that treatment. Only the impact strength increased in the composites with alkali-treated sisal fibers.

Desevolvimento de nanocompósitos de poli(metacrilato de metila)/argila processados por mistura no estado fundido

Poly(methyl methacrylate)/clay nanocomposites were prepared by melt mixing using a montmorillonite-rich clay (MMT). The clay in natura was treated with acrylic acid to facilitate the dispersion in the polymer matrix. A masterbatch of PMMA/clay was prepared and combined with the pure PMMA and then subjected to extrusion process using singlescrew and twin-screw extruders followed by injection. Nanocomposites were processed with clay contents of 1, 3, 5 and 8 wt.%. The effect of shear processing on the morphology of the nanocomposites was evaluated by XRD, SEM and TEM. Thermal and mechanical properties of the nanocomposites were investigated through TGA, DSC, HDT, VICAT, tensile and impact tests, to evaluate the effect of the addition of clay to the PMMA matrix. Flammability tests were also conducted to investigate the effect of the addition of clay on the flame retardation properties. SEM images of the nanocomposites indicated the presence of clay agglomerates, which resulted in the reduction of properties such as thermal stability, mechanical strength and impact resistance, and increased the rate of burning for materials processed by both extrusion routes

Estudo morfológico da blenda polimérica poli(metacrilato de metila)/poli(tereftalato de etileno) reciclado (PMMA/PET)

Among the options for plastics modification more convenient, both from a technical-scientific and economic, is the development of polymer blends by processing in the molten state. This work was divide into two stages, with the aim to study the phase morphology of binary blend PMMA / PET blend and this compatibilized by the addition of the poly(methyl methacrylate-co-glycidyl methacrylate-co-ethyl acrylate) copolymer (MMA-GMA-EA). In the first stage is analyzed the morphology of the blend at a preliminary stage where we used the bottle-grade PET in a Haake torque rheometer and the effect of compatibilizer in this blend was evaluated. In the second stage the blend was processed using the recycled PET in a single screw extruder and subsequently injection molding in the shape of specimens for mechanical tests. In both stages we used a transmission electron microscopy (TEM) to observe the morphologies of the samples and an image analyzer to characterize them. In the second stage, as well as analysis by TEM, tensile test, scanning electron microscopy (SEM) and atomic force microscopy (AFM) was performed to correlate the morphology with the mechanical properties. The samples used in morphological analyzes were sliced by cryo-ultramicrotomy technique for the analysis by TEM and the analysis by SEM and AFM, we used the flat face of the block after cut cryogenic. It was found that the size of the dispersed phase decreased with the addition of MMA-GMA-EA in blends prepared in a Haake. In the tensile test, the values of maximum tensile strength and modulus of elasticity is maintained in a range between the value of pure PMMA the pure PET, while the elongation at break was influenced by the composition by weight of the PMMA mixture. The coupling agent corroborated the results presented in the blend PMMA / PETrec / MMA-GMA-EA (80/15/5 %w/w), obtained by TEM, AFM and SEM. It was concluded that the techniques used had a good morphologic correlation, and can be confirmed for final analysis of the morphological characteristics of the blends PMMA / PET

O efeito do tratamento da atapulgita no desenvolvimento de compósito com o polietileno reciclado

The study aimed at the treatment of attapulgite for the development and characterization of composite recycled low density polyethylene - PEBD_rec embedded with natural attapulgite - ATP_NAT, sifted - ATP_PN and attapulgite treated with sulfuric acid - ATP_TR in different compositions (1, 3 and 5%) and compared with the PEBD_rec. The atapulgitas, natural, screened and treated, were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), particle size analysis, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and determining the area specific surface (BET). The composites were characterized by thermogravimetry (TG), differential scanning calorimetry (DSC), Xray diffraction (XRD), torque rheometry, scanning electron microscopy (SEM) and traction. The composite PEBD_rec / ATP (natural, sieved and treated) were produced by mixing in the molten state in a single screw extruder matrix wire with subsequent reprocessing matrix tape. It was found that the screening of attapulgite not reduce the quantity of quartz and the acid treatment completely extracted dolomite aggregate impurities of the channels attapulgite, and increase their surface area. The addition of attapulgite in PEBD_rec acts as a catalyst, reducing the thermal stability of the polymer. The increased concentration of attapulgite, increases resistance and reduces the elongation at break and modulus of elasticity of the composite PEBD_rec / attapulgite

Desenvolvimento e caracterização de compósitos poli(tereftalato de etileno) reciclado (PET reciclado) com flocos de vidro.

The growing concern with the solid residues management, observed in the last decade, due to its huge amount and impact, has motivated the search for recycling processes, where these residues can be reprocessed to generate new products, enlarging the cycle of materials and energy which are present. Among the polymeric residues, there is poly (ethylene terephthalate) (PET). PET is used in food packaging, preferably in the bottling of carbonated beverages. The reintegration of post-consumer PET in half can be considered a productive action mitigation of environmental impacts caused by these wastes and it is done through the preparation of several different products at the origin, i.e. food packaging, with recycling rates increasing to each year. This work focused on the development and characterization mechanical, thermal, thermo-mechanical, dynamic mechanical thermal and morphology of the pure recycled PET and recycled PET composites with glass flakes in the weight fraction of 5%, 10% and 20% processed in a single screw extruder, using the following analytical techniques: thermogravimetry (TG), differential scanning calorimetry (DSC), tensile, Izod impact, Rockwell hardness, Vicat softening temperature, melt flow rate, burn rate, dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The results of thermal analysis and mechanical properties leading to a positive evaluation, because in the thermograms the addition of glass flakes showed increasing behavior in the initial temperatures of thermal decomposition and melting crystalline, Furthermore was observed growing behavior in the mechanical performance of polymer composites, whose morphological structure was observed by SEM, verifying a good distribution of glass flakes, showing difference orientation in the center and in the surface layer of test body of composites with 10 and 20% of glass flakes. The results of DMTA Tg values of the composites obtained from the peak of tan ä showed little reductions due to poor interfacial adhesion between PET and recycled glass flakes.

Efeito da adição do poli(etileno acrilato de metila) (ema) e da fibra de linter de algodão nas propriedades do poli(tereftalato de etileno) reciclado (petrec)

The development of new materials to fill the demand of technological advances is a challenge for many researchers around the world. Strategies such as making blends and composites are promising alternatives to produce materials with different properties from those found in conventional polymers. The objective of this study is to evaluate the effect of adding the copolymer poly(ethylene methyl acrylate) (EMA) and cotton linter fibers (LB) on the properties of recycled poly(ethylene terephthalate) (PETrec) by the development of PETrec/EMA blend and PETrec/EMA/LB blend composite. In order to improve the properties of these materials were added as compatibilizers: Ethylene - methyl acrylate - glycidyl methacrylate terpolymer (EMA-GMA) and maleic anhydride grafted polyethylene (PE-g-MA). The samples were produced using a single screw extruder and then injection molded. The obtained materials were characterized by thermogravimetry (TG), melt flow index (MFI) mensurements, torque rheometry, pycnometry to determinate the density, tensile testing and scanning electron microscopy (SEM). The rheological results showed that the addition of the EMA copolymer increased the viscosity of the blend and LB reduces the viscosity of the blend composite. SEM analysis of the binary blend showed poor interfacial adhesion between the PETrec matrix and the EMA dispersed phase, as well as the blend composite of PETrec/EMA/LB also observed low adhesion with the LB fiber. The tensile tests showed that the increase of EMA percentage decreased the tensile strength and the Young s modulus, also lower EMA percentage samples had increased the elongation at break. The blend composite showed an increase in the tensile strength and in the Young`s modulus, and a decrease in the elongation at break. The blend formulations with lower EMA percentages showed better mechanical properties that agree with the particle size analysis which showed that these formulations presented a smaller diameter of the dispersed phase. The blend composite mechanical tests showed that this material is stronger and stiffer than the blend PETrec/EMA, whose properties have been reduced due to the presence of EMA rubbery phase. The use of EMA-GMA was effective in reducing the particle size of the EMA dispersed phase in the PETrec/EMA blend and PE-g-MA showed evidences of reaction with LB and physical mixture with the EMA