Search

The processing conditions were varied during the production of polycarbonate-based composites with the multiwalled carbon nanotubes (MWCNTs) Baytubes ® C150 P (Bayer MaterialScience AG, Leverkusen, Germany), by melt mixing with an extruder on a laboratory scale. These included the screw design, rotation speed, throughput, feeding position and MWCNT content. Particular attention was paid to the shortening of the MWCNT length as a function of the conditions mentioned. It was found that there is a correlation between the applied specific mechanical energy (SME) during the melt mixing process and MWCNT dispersion, which was quantified by the agglomerate area ratio of the non-dispersed nanotubes based on optical microscopic analysis. The higher the SME value, the lower this ratio, which indicates better dispersion. Above an SME value of about 0.4 kWh/kg, no further improvement in dispersion was achieved. The MWCNT length, as measured by the quantitative analysis of TEM images of the MWCNTs dissolved from the composites, decreased with the SME value down to values of 44% of the original MWCNT length. At a constant loading of 3 wt.%, the tensile strength and tensile modulus were almost independent of the SME, while the elongation at break and notched impact strength showed an increasing trend. The variation in the feeding position showed that feeding the MWCNTs into a side feeder led to slightly better electrical and mechanical properties for both types of MWCNTs studied (Baytubes ® C150 P and Nanocyl™ NC7000 (Nanocyl S.A., Sambreville, Belgium)). However, feeding into the hopper led to better CNT dispersion with Baytubes ® C150 P, while this was the case with Nanocyl™ NC7000 when feeding into the side feeder. The screw profile had an influence on the dispersion, the MWCNT length and the electrical resistance, but only to a small extent. Distributive screws led to a greater shortening of the MWCNT length than dispersive screws. By varying the MWCNT content, it was shown that a greater MWCNT shortening occurred at higher loadings. Two-stage masterbatch dilution leads to stronger shortening than composite production with direct MWCNT incorporation.

Polypropylene (PP) is one of the most versatile polymers widely used in packaging, textiles, automotive, and electrical applications. Melt blending of PP with micro- and/or nano-fillers is a common approach for obtaining specific end-use characteristics and major enhancements of properties. The study aims to develop high-performance composites by filling PP with CaSO 4 β-anhydrite II (AII) issued from natural gypsum. The effects of the addition of up to 40 wt.% AII into PP matrix have been deeply evaluated in terms of morphology, mechanical and thermal properties. The PP-AII composites (without any modifier) as produced with internal mixers showed enhanced thermal stability and stiffness. At high filler loadings (40% AII), there was a significant decrease in tensile strength and impact resistance; therefore, custom formulations with special reactive modifiers/compatibilizers (PP functionalized/grafted with maleic anhydride (PP-g-MA) and zinc diacrylate (ZnDA)) were developed. The study revealed that the addition of only 2% ZnDA (able to induce ionomeric character) leads to PP-AII composites characterized by improved kinetics of crystallization, remarkable thermal stability, and enhanced mechanical properties, i.e., high tensile strength, rigidity, and even rise in impact resistance. The formation of Zn ionomers and dynamic ionic crosslinks, finer dispersion of AII microparticles, and better compatibility within the polyolefinic matrix allow us to explain the recorded increase in properties. Interestingly, the PP-AII composites also exhibited significant improvements in the elastic behavior under dynamic mechanical stress and of the heat deflection temperature (HDT), thus paving the way for engineering applications. Larger experimental trials have been conducted to produce the most promising composite materials by reactive extrusion (REx) on twin-screw extruders, while evaluating their performances through various methods of analysis and processing.

The acoustic melt stream velocity field, total force, and trajectory of fluorescent particles in the plasticizing chamber were analyzed using finite element simulation to investigate the acoustic streaming and mixing characteristics in ultrasonic plasticization micro-injection molding (UPMIM). The fluorescence intensity of ultrasonic plasticized samples containing thermoplastic polymer powders and fluorescent particles was used to determine the correlation between UPMIM process parameters and melt mixing characteristics. The results confirm that the acoustic streaming driven mixing occurs in ultrasonic plasticization and could provide similar shear stirring performance as the screw in traditional extrusion/injection molding. It was found that ultrasonic vibrations can cause several melt vortices to develop in the plasticizing chamber, with the melt rotating around the center of the vortex. With increasing ultrasonic amplitude, the melt stream velocity was shown to increase while retaining the trace, which could be altered by modulating other parameters. The fluorescent particles are subjected to a two-order-of-magnitude stronger Stokes drag force than the acoustic radiation force. The average fluorescence intensity was found to be adversely related to the distance from the sonotrodes' end surface, and fluorescence particles were more equally distributed at higher parameter levels.

Co-continuous blend systems of polycarbonate (PC), poly(styrene- co -acrylonitrile) (SAN), commercial non-functionalized multi-walled carbon nanotubes (MWCNTs) or various types of commercial and laboratory functionalized single-walled carbon nanotubes (SWCNTs), and a reactive component (RC, N- phenylmaleimide styrene maleic anhydride copolymer) were melt compounded in one step in a microcompounder. The blend system is immiscible, while the RC is miscible with SAN and contains maleic anhydride groups that have the potential to reactively couple with functional groups on the surface of the nanotubes. The influence of the RC on the localization of MWCNTs and SWCNTs (0.5 wt.%) was investigated by transmission electron microscopy (TEM) and energy-filtered TEM. In PC/SAN blends without RC, MWCNTs are localized in the PC component. In contrast, in PC/SAN-RC, the MWCNTs localize in the SAN-RC component, depending on the RC concentration. By adjusting the MWCNT/RC ratio, the localization of the MWCNTs can be tuned. The SWCNTs behave differently compared to the MWCNTs in PC/SAN-RC blends and their localization occurs either only in the PC or in both blend components, depending on the type of the SWCNTs. CNT defect concentration and surface functionalities seem to be responsible for the localization differences.

Biocomposites based on poly(lactic acid) (PLA) and biochar (BC) particles derived from spent ground coffee were prepared using two different processing routes, namely melt mixing and solvent casting. The formulated biocomposites were characterized through rheological, thermal, and mechanical analyses, aiming at evaluating the effects of the filler content and of the processing method on their final properties. The rheological characterization demonstrated the effectiveness of both exploited strategies in achieving a good level of filler dispersion within the matrix, notwithstanding the occurrence of a remarkable decrease of the PLA molar mass during the processing at high temperature. Nevertheless, significant alterations of the PLA rheological behavior were observed in the composites obtained by melt mixing. Differential scanning calorimetry (DSC) measurements indicated a remarkable influence of the processing method on the thermal behavior of biocomposites. More specifically, melt mixing caused the appearance of two melting peaks, though the structure of the materials remained almost amorphous; conversely, a significant increase of the crystalline phase content was observed for solvent cast biocomposites containing low amounts of filler that acted as nucleating agents. Finally, thermogravimetric analyses suggested a catalytic effect of BC particles on the degradation of PLA; its biocomposites showed decreased thermal stability as compared with the neat PLA matrix.

Graphene-based materials are a family of carbonaceous structures that can be produced using a variety of processes either from graphite or other precursors. These materials are typically a few layered sheets of graphene in the form of platelets and maintain some of the properties of pristine graphene (such as two-dimensional platelet shape, aspect ratio, and graphitic bonding). In this work we present melt mixed graphene-based polypropylene systems with significantly reduced percolation threshold. Traditionally melt-mixed systems suffer from poor dispersion that leads to high electrical percolation values. In contrast in our work, graphene was added into an isotactic polypropylene matrix, achieving an electrical percolation threshold of ~1 wt.%. This indicates that the filler dispersion process has been highly efficient, something that leads to the suppression of the β phase that have a strong influence on the crystallization behavior and subsequent thermal and mechanical performance. The electrical percolation values obtained are comparable with reported solution mixed systems, despite the use of simple melt mixing protocols and the lack of any pre or post-treatment of the final compositions. The latter is of particular importance as the preparation method used in this work is industrially relevant and is readily scalable.

Small-scale melt mixing was performed for composites based on polypropylene (PP) and 0.5⁻7.5 wt % multiwalled carbon nanotubes (MWCNT) to determine if masterbatch (MB) dilution is a more effective form of nanofiller dispersion than direct nanotube incorporation. The methods were compared using composites of five different PP types, each filled with 2 wt % MWCNTs. After the determination of the specific mechanical energy (SME) input in the MB dilution process, the direct-incorporation mixing time was adjusted to achieve comparable SME values. Interestingly, the electrical resistivity of MB-prepared samples with 2 wt % MWCNTs was higher than that of those prepared using direct incorporation-despite their better dispersion-suggesting more pronounced MWCNT shortening in the two-step procedure. In summary, this study on PP suggests that the masterbatch approach is suitable for the dispersion of MWCNTs and holds advantages in nanotube dispersion, albeit at the cost of slightly increased electrical resistivity.

Biodegradable potato starch/PVA samples containing different concentrations of rosin were prepared by melt-mixing in order to study the enhancement of the properties of native starch films. Glycerol and polyvinyl alcohol (PVA) are commonly used as plasticizers of starch. Their relatively low molecular weight (compared with starch) contributes to a good processability. Rosin is a renewable product whose incorporation in the starch/PVA matrix induces processing aid and reinforcing effects. Its relatively high molecular weight might prevent its migration to the surface of the final product. Water content, solubility in water, mechanical properties, microstructure and dynamic mechanical analysis of the samples were studied. The addition of 8% rosin to starch/PVA blends led to tensile strength values higher than 10 MPa and elongation at break values close to 2000%, values comparable to those offered by conventional polymers used in food packaging, for example LDPE. Furthermore, starch compounds have low cost and high biodegradability., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The aim of the present study was to evaluate the thermodynamic properties of in-situ formation of cocrystal formulations by the melt-mixing method. Specifically, the thermodynamic mixing behaviour of carbamazepine-nicotinamide and ibuprofen-nicotinamide cocrystals prepared with the aid of Soluplus ® (SOL) were evaluated using thermodynamic lattice-based solution theories. Thermodynamic miscibility of both cocrystals with SOL was predicted by calculating Gibb's free energy based on the Flory-Huggins (FH) interaction parameter (χ), while the activity coefficient of cocrystals estimated with the aid of solid-liquid equilibrium equation and FH lattice theory, showed good thermodynamic miscibility of the components at elevated temperatures used normally during melt-mixing based processes. Complete phase transition diagrams constructed with the aid of DSC measurements and FH solution theory, suggested the existence of two transition zones: (1) a stable cocrystal zone, located at the right-hand-side of the spinodal phase separation curve, where stable cocrystals are prepared and (2) an unstable cocrystal zone, located at the left-hand-side of the spinodal curve up to liquidus, where the matrixforming polymer sets a kinetic barrier to recrystallization and hence, a barrier to the formation of cocrystals. The validity of the suggested thermodynamic phase transition zones was experimentally verified by ATR-FTIR and hot-stage polarized light microscopy., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this work, design and development of a new melt mixing method and corresponding mixer for polymer materials were reported. Effects of ultrasonic power and sonication time on the carbon nanotubes (CNTs) filled ultra high molecular weight polyethylene (UHMWPE) nanocomposites were experimentally studied. Transmission Electron Microscopy images showed that homogeneous dispersion of CNTs in intractable UHMWPE matrix is successfully realized due to the synergetic effect of ultrasonic wave and extensional deformation without any aid of other additives or solvents. Differential scanning calorimetry results revealed an increase in crystallinity and crystallization rate due to the finer dispersion of the CNTs in the matrix which act as nucleating point. Composites' complex viscosity and storage modulus decreased sharply at first and then leveled off with the increase of sonication time or the ultrasonic power. The thermal stability and the tensile strength of the CNTs/UHMWPE nanocomposites improved by using this novel mixing method. This is the first method that combined the ultrasonic wave and the extensional deformation in which the elongation rate, sonication time and ultrasonic power can be adjusted simultaneously during mixing. The novel mixer offers several advantages such as environment-friendly, high mixing efficiency, self-cleaning and wide adaptability to materials., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The purpose of the present study was to use commercial available polymers like PVP/PEG, soluplus® and kollidon® SR to prepare immediate and sustained release formulations of felodipine by hot melt mixing method. Solid dispersions containing 5, 10, 20 and 30wt% drug have been prepared in a Haake-Buchler Reomixer at melt temperature 130°C and mixing time 10min. As was found from DSC and XDR studies completely amorphous and miscible solid dispersions can be prepared. In all cases a single glass transition was recorded, which is depended from the used drug amount. Hydrogen bonds and the molecular interaction between felodipine and polymer matrices are responsible for the miscibility of prepared formulations. This has as result the substantial enhancement of felodipine release rate in PVP/PEG mixture and due to the high solubility of used polymers immediate release formulations have been prepared. On the contrary, sustained release formulations can be prepared in the case of kollidon SR solid dispersions. The release mechanism of all preparations was studied using different kinetic models. Finally, binding affinity values calculated by molecular docking simulations were used as estimators for predicting long-term drug's physical stability in solid dispersions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A novel bi-layered multiphasic scaffold (BLS) have been fabricated for the first time by combining melt mixing, compression molding and particulate leaching. One layer has been composed by polylactic acid (PLA) presenting pore size in the range of 90-110µm while the other layer has been made of polycaprolactone (PCL) with pores ranging from 5 to 40µm. The different chemo-physical properties of the two biopolymers combined with the tunable pore architecture permitted to realize monolithic functionally graded scaffolds engineered to be potentially used for interface tissues regenerations. BLS have been characterized from a morphological and a mechanical point of view. In particular, mechanical tests have been carried out both in air and immersing the specimens in phosphate buffered saline (PBS) solution at 37°C, in order to evaluate the elastic modulus and the interlayer adhesion strength. Fibroblasts and osteoblasts have been cultured and co-cultured in order to investigate the cells permeation trough the different layers. The results indicate that the presented method is appropriate for the preparation of multiphasic porous scaffolds with tunable morphological and mechanical characteristics. Furthermore, the cells seeded were found to grow with a different trend trough the different layers thus demonstrating that the presented device has good potential to be used in interface tissue regeneration applications., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The actinomycetes, Gram-positive filamentous bacteria, are the most prolific source of natural occurring antibiotics. At an industrial level, antibiotics from actinomycete strains are produced by means of submerged fermentations, where one of the major factors negatively affecting bioproductivity is the pellet-shaped biomass growth. The immobilization of microorganisms on properly chosen supports prevents cell-cell aggregation resulting in improving the biosynthetic capability. Thus, novel porous biopolymer-based devices are developed by combining melt mixing and particulate leaching. In particular, polycaprolactone (PCL), polyethylene glycol (PEG), and sodium chloride (NaCl) with different grain sizes are used to prepare PCL/PEG/NaCl blends in the melt. These blends are then leached to obtain PCL-based porous membranes that are used as solid support for the growth of Streptomyces coelicolor, a model streptomycete used to produce various antibiotics including the blue colored actinorhodin (ACT). Thereafter, the effect of the devices' characteristics on the bacterial growth and on the production ACT is evaluated. The results showed that ACT production is strongly dependent on the pore size distribution of the device. Moreover, membranes with pores ranging from 90 to 110 μm are able to offer a potential improvement in volumetric productivity of ACT if compared to conventional submerged liquid culture., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Interface tissue engineering (ITE) is used to repair or regenerate interface living tissue such as for instance bone and cartilage. This kind of tissues present natural different properties from a biological and mechanical point of view. With the aim to imitating the natural gradient occurring in the bone-cartilage tissue, several technologies and methods have been proposed over recent years in order to develop polymeric functionally graded scaffolds (FGS). In this study three-layered scaffolds with a pore size gradient were developed by melt mixing polylactic acid (PLA) and two water-soluble porogen agents: sodium chloride (NaCl) and polyethylene glycol (PEG). Pore dimensions were controlled by NaCl granulometry while PEG solvation created a micropores network within the devices. Scaffolds were characterized from a morphological and mechanical point of view in order to find a correlation between the preparation method, the pore architecture and compressive mechanical behavior. Biological tests were also performed in order to study the effect of pore size gradient on the permeation of different cell lines in co-culture. To imitate the physiological work condition, compressive tests were also performed in phosphate buffered saline (PBS) solution at 37°C. The presented preparation method permitted to prepare three-layered scaffolds with high control of porosity and pore size distribution. Furthermore mechanical behaviors were found to be strongly affected by pore architecture of tested devices as well as the permeation of osteoblast and fibroblast in-vitro., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The effect of plasticizer's (PEG) molecular weight (MW) on PVP based solid dispersions (SDs), prepared by melt mixing, was evaluated in the present study using Tibolone as a poorly water soluble model drug. PEGs with MW of 400, 600, and 2000 g/mol were tested, and the effect of drug content, time and temperature of melt mixing on the physical state of Tibolone, and the dissolution characteristics from SDs was investigated. PVP blends with PEG400 and PEG600 were completely miscible, while blends were heterogeneous. Furthermore, a single Tg recorded in all samples, indicating that Tibolone was dispersed in a molecular lever (or in the form of nanodispersions), varied with varying PEG's molecular weight, melt mixing temperature, and drug content, while FTIR analysis indicated significant interactions between Tibolone and PVP/PEG matrices. All prepared solid dispersion showed long-term physical stability (18 months in room temperature). The extent of interaction between mixture components was verified using Fox and Gordon-Taylor equations. Artificial neural networks, used to correlate the studied factors with selected dissolution characteristics, showed good prediction ability., (Copyright © 2013 Elsevier B.V. All rights reserved.)