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The aim of the present article is to study the different phenomena which are at the basis of the consolidation of commingled thermoplastic semi-pregs made of amorphous polyester fibers and E-glass reinforcement. The evolution of the void fraction during the consolidation of the composite was monitored by a dynamometer, equipped with parallel plates and a forced convection oven. Different physical changes were associated to the consolidation temperature. Scanning electron microscopy (SEM) and thermomecahnical analysis (TMA) showed that at low temperature, matrix fiber deformation and sintering are responsible of the initial void reduction. At a temperature higher than the onset of the flow region, reinforcement impregnation is responsible of the further void reduction. Dimensionless analysis confirmed that at lower temperatures, corresponding to higher viscosities, consolidation due to viscous flow of the polymer matrix is negligible compared to consolidation due to sintering of matrix fibers. The results indicate that the Darcy law can efficiently represent the consolidation during the microscale impregnation of the reinforcement, but cannot account for the initial stages of consolidation. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers

This work is aimed to the development and property optimization of cardanol derived plasticizers. To this purpose, different plasticizers were produced though different epoxidation routes, characterized by low toxicological and environmental impact. The plasticizers are characterized by different yield of epoxidation of the alkyl chain double bonds. The properties of the cardanol derived plasticizers were compared to the properties of commercial plasticizers, either phthalates or natural derived. Mechanical properties of soft PVC plasticized by cardanol derivatives were shown to be comparable to those of PVC with commercial plasticizers. The plasticizing efficiency of cardanol derivatives was significantly improved by increasing the yield of epoxidation. Also, mechanical properties performed after ageing showed the excellent stability of the properties of the cardanol derived plasticizer characterized by the higher yield. Evaluation of the property retention index after ageing indicated that such plasticizers showed an improved stability of properties compared to other commercial plasticizer. The results obtained highlight the relevance of an high conversion of the double bonds into epoxies in order to produce high quality plasticizers.

Focused on biomedical applications of thermo-responsive polymers, low-doses of gamma radiation from a 60Co source were applied in a simple one-pot method to synthesize graft copolymers of alginate and poly(N-isopropylacrylamide) (PNIPAAm) with different compositions. The molar percentage of grafted NIPAAm (% molar NIPAAm) was determined by thermogravimetric analysis (TGA) and elemental analysis (EA), being the copolymer structure-property relationship studied in terms of thermo-associative and rheological behavior in aqueous solutions. The addition of more NIPAAm monomer in the initial mixture of reaction, as well as, increasing absorbed dose lead to a greater grafting. However, increasing radiation dose produces copolymers with diminished viscoelastic properties caused by the alginate backbone scission. From rheological curves, two transition temperatures, Ta and Tgel, were determined as a consequence of the thermo-responsiveness of PNIPAAm side chain. Storage (G′) and loss (G″) modulus curves undergo a slope inversion at Ta temperature, where both moduli begin to increase caused by an associative behavior of PNIPAAm domains. While, Tgel temperature is related to the onset of the gelation process at the G′/G″ crossover. In order to design samples with liquid-gel transitions close to the human body, able to form gels in situ once inoculated, it was possible to tailor both transition temperatures selecting copolymers with an appropriate PNIPAAm content and optimizing the copolymer concentration in the aqueous solution. A good agreement between transition temperatures and viscoelastic properties was achieved for 5 wt% aqueous solutions of copolymers with low NIPAAm content synthesized at the lowest absorbed dose (0.5 kGy). Fil: Lencina, María Malvina Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina Fil: Rizzo, Chiara. University of Salento; Italia Fil: Demitri, Chistian. University of Salento; Italia Fil: Andreucetti, Noemi Amalia. Universidad Nacional del Sur. Departamento de Química; Argentina Fil: Maffezoli, Alfonso. University of Salento; Italia

This work is aimed at studying the suitability of polylactic acid (PLA) plasticized by two cardanol derivatives, i.e., cardanol and epoxidized cardanol acetate, in rotational molding, for the production of hollow items. For this purpose, plasticized PLA samples were obtained by melt mixing and then processed by a lab-scale rotational molding equipment. For comparison, poly(ethylene glycole), PEG, and plasticized PLA samples were also produced. Despite the very low cooling rates attained in rotational molding, completely amorphous samples were obtained with neat PLA and PLA plasticized by cardanol derivatives. In contrast, PEG plasticized PLA showed a very high degree of crystallinity, as highlighted by DSC and XRD analysis, which made the extraction of the rotomolded box-shaped specimens impossible. The plasticizing effectiveness of cardanol derivatives was proven by tensile testing of rotational molded prototypes, which highlighted the reduced modulus and strength and improved strain to break, compared to neat PLA. Therefore, efficient toughening of PLA can be attained by the use of the two cardanol derived plasticizers, which involves a significant reduction of the polymer glass transition, as well as a reduced increase of the crystallization kinetic. On the other hand, the reduction of the glass transition temperature due to the addition of plasticizer is responsible for significant crystallization effects even during ageing at room temperature, which involves significant embrittlement of the material.

Bioactive food-preserving materials are based on the use of a natural antimicrobial compound loaded in a carrier material, which is able to trigger its release when requested and to modulate the rate of release, thus using either toxic or inhibitory properties against pathogens or bacteria due to food decomposition. In this study, the Schiff base formation for chitosan functionalization was achieved by the reaction of chitosan with cinnamaldehyde at different concentrations. Cinnamaldehyde is an aromatic α,β-unsaturated aldehyde, and the major component in essential oils from some cinnamon species. It has been shown to exert antimicrobial action against a large number of microorganisms including bacteria, yeasts, and mould. The formation of the Schiff base is reversible under suitable conditions, and this might allow the release of the active cinnamaldehyde from chitosan, used as the carrier. The reaction kinetics was investigated by means of rheological measurements, while infrared spectroscopy was used to assess the efficacy of the functionalization. The addition of nanometric graphene stacks to the cinnamaldehyde-functionalized chitosan films was evaluated with the aim to increase the mechanical properties of the film. Finally, the films were tested for antifungal properties with bread slices against a selected mould line.

The mechanical and electrochemical behavior of ultrasonic spot welded hybrid joints, made of AA5754 aluminum and carbon fiber reinforced epoxy with a co-cured thermoplastic surface layer, was studied. The effect of the welding parameters (energy and force) and the thickness of a thermoplastic film, applied as an upper ply in the composite lay-up, on the development of adhesion strength, was investigated. The best mechanical results were obtained when the welding parameters were able to achieve a large bonding area of mechanical interlocking between naked carbon fibers and aluminum and a better load distribution. The electrochemical results excluded the possibility of galvanic corrosion between aluminum and composite adherends thanks to the insulating action provided by the thermoplastic film.

Stress relaxation behavior of unidirectional AS4/8852 carbon/epoxy composites at high temperatures has been investigated. Specimens with an off axis angle of 90° and ±45° have been exposed to constant strain and high temperature. The mechanical results have been modeled by Standard Linear Solid model. The obtained parameters have been implemented in a finite element (FEM) model able to predict the residual stresses in carbon fiber reinforced composites, both in the elastic and in the viscoelastic field.Stress relaxation behavior of unidirectional AS4/8852 carbon/epoxy composites at high temperatures has been investigated. Specimens with an off axis angle of 90° and ±45° have been exposed to constant strain and high temperature. The mechanical results have been modeled by Standard Linear Solid model. The obtained parameters have been implemented in a finite element (FEM) model able to predict the residual stresses in carbon fiber reinforced composites, both in the elastic and in the viscoelastic field.

The approach for joining thermosetting matrix composites (TSCs) proposed in this study is based on the use of a low melting co-cured thermoplastic film, added as a last ply in the stacking sequence of the composite laminate. During curing, the thermoplastic film partially penetrates in the first layer of the thermosetting composite, leading to macro-mechanical interlocking as the main connection mechanism between the thermoplastic film and the underlying composite. After curing, the thermosetting composite joints with the thermoplastic modified surface can be assembled by welding. Welding of the TSC-TSC joints is performed by ultrasonic and induction welding. The weld strength is investigated by morphological characterization of cross sections and failure surfaces and by mechanical testing. The effect of the thermoplastic film thickness on the welding process and on its outcome is also analyzed. Both induction and ultrasonic welding mostly result in good-quality welded joints. The welding process used as well as the initial thickness of the thermoplastic film are found to have a significant effect on the final thickness of the weld line and on the location of failure. Thicker thermoplastic films are found to ease the welding processes.

The engineering aspects, which are associated with the development of nanocomposites, involve in either final properties or processability of nanocomposites. Both are affected by the distribution of nanofiller in the matrix and by the aspect ratio of the nanofiller. A nanofilled thermosetting resin can be exploited as a matrix for continuous fibers when the alignment of a high aspect ratio nanofiller is achieved, and in this case, a hierarchical composite is obtained. In this study, a new procedure for the alignment of nanofillers in a thermosetting matrix is proposed. The two-step approach is based on (i) the alignment of nanofillers (carbon nanotubes, graphene, etc.) in thermoplastic fibers by a fiber spinning process and (ii) the use of these nanocomposite fibers as a carrier to bring aligned nanofillers into a reactive thermosetting resin. These fibers, soluble in the thermosetting resin, release the nanofillers orientated according to the direction in which fibers are positioned, even after the curing of the matrix. The proof of concept is demonstrated by producing melt spun polyethylene terephtalate (PETg) fibers filled with graphene nanoplatelets (GNP) and multiwall carbon nanotubes (MWCNT) with a very high filler content (up to 10 wt%) in view of producing a hierarchical composite. POLYM. COMPOS., 36:1096–1103, 2015. © 2015 Society of Plastics Engineers

Ultrasonic metal welding has been applied for joining aluminum AA5754 sheets to a thermoset matrix composite consisting in a carbon fiber reinforced epoxy resin (CF/epoxy). To overcome the limitations of thermosetting resins, that, unlike thermoplastic polymers, cannot melt due to their chemical structure, a thermoplastic film of Polyamide 6 (PA6) has been used as a surface layer of the CF/epoxy stack before curing. The functional surface created on the thermoset matrix composite enables a fast welding with a metallic sheet. By a proper selection of welding energy and force, an average adhesion strength of 34.8 MPa has been obtained on CF/epoxy-PA6-AA5754 ultrasonically welded joints. The morphological characterization has revealed that the aluminum-composite interface is characterized by carbon fibers in a direct contact or even embedded in aluminum, whose surface presents pores and crevices due to the pronounced plastic deformation of the Al interfacial area.

Skeletal defects reconstruction, using custom-made substitutes, represents a valid solution to replacing lost and damaged anatomical bone structures, renew their original function, and at the same time, restore the original aesthetic aspect. Rapid prototyping (RP) techniques allow the construction of complex physical models based on 3D clinical images. However, RP machines usually work with synthetic polymers; therefore, producing custom-made scaffolds using a biocompatible material directly by RP is an exciting challenge. The aim of the present work is to investigate the potentiality of 3D printing as a manufacturing method to produce an osteogenic hydroxyapatite-polylactic acid bone graft substitute.

Transparent nanocomposite films were prepared using bacterial cellulose (BC) as reinforcement and diethylene glycol bis(allyl carbonate) polymer (DEAC) as matrix by vacuum infiltration and UV polymerization. The BC/DEAC nanocomposites exhibit excellent transparency up to 88% at wavelength of 550 nm. The uniform dispersion of resin in BC 3D network was evidenced from SEM and ATR-FTIR analyses, confirms the complete photo-polymerization of diethylene glycol bis(allyl)carbonate monomer to Poly (diethylene glycol bis(allyl carbonate) in BC network. The BC/DEAC composites have good mechanical properties, reaching a tensile strength of 130 MPa and a Young’s Modulus of 6.4 GPa. Applying a micromechanic modeling approach, the elastic modulus of the composite was used in order to determine the average aspect ratio of BC fibers. These flexible transparent BC/DEAC composite films can be considered as functional films for optoelectronics application.

Ultrasonic propagation was used to provide heat and pressure in order to perform impregnation and consolidation during production of thermoplastic matrix composites. For this purpose, a new experimental set-up, integrating a laboratory filament winding machine with a horn and a compaction roller, was developed. The heat transfer phenomena occurring during continuous impregnation and consolidation were simulated solving by finite element (FE) analysis the energy balance equations in 2D accounting for the heat generated by ultrasonic waves, the melting characteristics of the matrix and the movement of the thermoplastic commingled roving. The temperature distribution in the composite, predicted by the numerical simulations, was validated by temperature measurements during the production of E-glass/polypropylene cylinders, with the optimized parameters obtained by the FE analysis. The ultrasonic consolidated composite cylinders were characterized by low void content and a shear modulus comparable with that obtained by the micromechanical analysis.

A simple procedure for the alignment of graphene nanoplatelets (GNPs) in a thermosetting matrix is presented. First, the alignment of GNPs in thermoplastic fibers of amorphous polyetylene terephthalate (aPET) is achieved by a fiber spinning process. The nanocomposite fibers, obtained with a very high filler content (10 wt%), are then transferred into a reactive epoxy resin. After dissolution of aPET, the nanofillers remained oriented in the thermosetting matrix. The characterization of the obtained nanocomposites has been carried by means of different experimental techniques which provided complementary results. The proposed method has the potential to be used in the manufacturing of hierarchical composites, by introducing nanofilled microfibers into continuous fibers reinforced composites.

The need for new measurement techniques able to assess the nanofiller dispersion is still receiving great consideration when nanocomposites are developed. This occurs since different routes to disperse nanostructures generate molecular changes in polymer matrices that promote complex polymer–polymer and polymer–nanofiller interactions, which make difficult a suitable estimation of the dispersion. In this paper, ultrasonic waves at different frequencies and power were used for preparing nanocomposite samples and for evaluating the nanofiller dispersion. First, a patented method was used to disperse multiwall carbon nanotubes (MWCNTs) in polyamide 12 through extrusion assisted by low-frequency and high power ultrasound (with frequency ranging between 20 and 50 kHz). This “green” processing method was able to induce different states of dispersion of the nanofillers, as well as chemical modifications to polymer chains promoting branching reactions. Then, ultrasonic dynamic mechanical analysis (UDMA with ultrasound frequency in the megahertz range) was used to estimate the dispersion of the different nanocomposite samples. Compared to rheological measurement methods, UDMA provided a better estimation of the quality of dispersion, being sensitive both to the complex molecular architectures in polymer matrices and to the scattering due to MWCNT agglomerates.

The aim of this work is to study the effect of an organically modified clay on the structural relaxation behavior of an amorphous thermoplastic matrix. Differential scanning calorimetry (DSC) and pressure–volume–temperature (PVT) analysis were used in order to calculate the relaxation enthalpy and specific volume of the neat matrix and the nanocomposite during ageing below the glass transition region. Stress relaxation experiments were used to measure the characteristic relaxation time of the materials at different temperatures below glass transition. DSC and PVT analysis both revealed that relaxation phenomena are more relevant for the nanocomposite compared to the neat matrix. This result was confirmed by stress relaxation measurements, which indicates that below the glass transition the relaxation times of the nanocomposite are lower than those of the neat matrix. The enhanced relaxation behavior of the nanocomposite compared to the neat matrix was attributed to the presence of the organic modifier, which, acting as a plasticizer for the matrix, enhances its molecular mobility. The presence of low glass transition portions in the matrix was also evidenced by DSC and dynamic mechanical analysis.

An overview of the current state of art of the ultrasonic treatment technology applied to polymer melts is presented. The research and technological advancements of the ultrasonic treatment as applied to development of polymeric materials are discussed. An analysis of the technological progress shows that the mechanism of the effects of ultrasound on polymer melts is not fully understood at present. Such lack in fully understanding the mechanism could limit the use of this versatile technology in future applications. Based on the critical analysis of the research progress to date, some key issues for a deeper understanding of the chemical and physical effects of ultrasound on polymer melts are identified. © 2012 Wiley Periodicals, Inc. Adv Polym Techn 32: E582–E602, 2013; View this article online at wileyonlinelibrary.com. DOI 10.1002/adv.21303

The aim of this work was to develop polyamide-6/ organic-modified montmorillonite (omMMT) nanocomposites for the production of hollow parts by rotational molding. Particular emphasis was placed on the mechanical and flame retardancy properties needed for the fabrication of vessels for flammable liquids. The morphology of the melt compounded nanocomposites, produced by melt compounding, was investigated by X-ray diffraction measurements (WAXD), and Transmission Electron Microscopy (TEM) showed an exfoliated structure. Rheological measurements were used in order to verify whether the viscosity of materials was adequate for rotational molding. While thermomechanical analysis has revealed that neat PA6 and its nanocomposites were not suitable for rotational molding, due to the very low thermal stability of the polymer, the addition of a thermal stabilizer, shifted the onset of degradation to higher temperatures, thus widening the processing window of both PA6 and PA6 nanocomposites. Large-scale vessel prototypes were obtained by rotational molding of thermo-stabilized PA6 and its nanocomposites, and samples extracted from the rotomolded parts were characterized with respect to physical and mechanical properties. It was found that the PA6 nanocomposites exhibited significant improvements at cone calorimeter tests in comparison with neat PA6.

The objective of this work is to study the sintering behavior of polyamide 6 (PA6) powders and PA6 nanocomposites by means of thermomechanical (TMA) and dimensionless analysis in view of its technological application in rotational molding. TMA analysis was used to monitor the bulk density evolution of PA6 powders and PA6 nanocomposites when heated above the melting temperature. Experimental TMA results indicate that the sintering of PA6 and PA6 nanocomposites occurs in two different steps, namely powder coalescence and void removal. Furthermore, TMA analysis also showed that relevant degradation phenomena occur during the sintering of PA6 and PA6 nanocomposites, leading to gas formation in the molten polymer. The suitability of these materials in rotational molding was then assessed by defining a processing window, as the temperature difference between the endset sintering and the onset degradation. The heating rate dependence of the processing window was explained by means of dimensionless analysis, showing that powder coalescence is influenced by the viscosity evolution of the matrix, whereas void removal is influenced by the gas diffusivity inside the molten matrix. Therefore, the diffusion activation energy correlates the endset sintering temperature to the heating rate. On the other hand, the onset degradation temperature depends on the heating rate, due to the characteristic activation energy of the degradation process. Accordingly, the width of the processing window mainly depends on the values of the activation energies for diffusivity and degradation. The width of the processing window for neat PA6 was found to be too narrow to candidate this polymer for rotational molding. The addition of nanofiller causes a narrowing of the processing window, whereas the PA6 matrix modified with a thermal stabilizer showed a sufficiently broad processing window, compatible for use in rotational molding

Differential scanning calorimetry was used to study the thermal characteristics and morphological structure of species produced during the ring opening polymerization of cyclic butylene terephthalate (CBT). Thermal programs consisting of a first ramp heating scan and an isothermal step, followed by cooling and a second ramp heating step, were used to study the effects of thermal history, catalyst (butyl chlorotin dihydroxide) at concentrations between 0.1 and 1.3% (w/w), and the presence of a layered silicate nanofiller (montmorillonite at 4.0%, w/w) on the structure of the resulting polymer (poly(butylene terephthalate), pCBT). Wide angle X-ray diffraction was used to monitor the degree of exfoliation of the nanocomposites. It was found that pCBT is formed in the amorphous state, and crystallizes during the heating step or during the isothermal step at temperatures lower than the equilibrium melting temperature of the polymer ( T m 0 ). When premixed with the nanofiller, irrespective of whether this was previously intercalated with a tallow surfactant or used in its pristine form, polymerization took place at higher temperatures and most of the crystallization was found to occur during the cooling stage. In those cases where crystallization took place during either the first heating scan, or during a prolonged isothermal step below the T m 0 of the polymer, the resulting crystals were found to have a higher lamellar thickness, as compared with the same polymer crystallized from the melt during the cooling step from temperatures above the polymer T m 0 .

In this work nanocomposite in a polyurethane (PU) matrix, using an organically modified montmorillonite (OMM), were studied. An amount of organoclay ranging from 2% up to 6% by volume was added to the polyol component of the resin before mixing with isocyanate. The basal distance of OMM before and after mixing with the polyol and after curing was characterized by X-ray diffraction. The glass transition temperature (Tg) of PU nanocomposites, measured using differential scanning calorimeter, increases with increasing the volume fraction of OMM. On the other hand, the heat capacity increment, ΔCp, decreases from that the unfilled PU to that of the sample with 5.7 vol.% of OMM. Therefore the rigid amorphous fraction of the PU nanocomposites increases with increasing volume fraction of OMM. Finally, a three-phase model similar to that applied to study semi-crystalline polymers, was used to analyze the intercalation of the PU chains between OMM lamellae. The definition of molecular cooperativity was discussed for these systems and the characteristic length of the cooperative region was determined, using Donth equation.

The potential improvement of physical and mechanical properties in nanostructured composites can be fully exploited by proper distribution of the nanofillers in the polymer matrix, which strongly affects both their final properties and processability. A nanofilled thermosetting polymer can be used as a matrix for continuous fibers when the alignment of a high aspect ratio nanofiller is achieved: in this case a hierarchical composite is obtained. In this work a new processing technology for the production of hierarchical polymer based composites is proposed. First, the alignment of graphene nanoplatelets (GNPs) in thermoplastic fibers of amorphous polyetylene terephthalate (PETg) is achieved by a fiber spinning process. The obtained nanocomposite fibers with a very high filler content (10 wt%) are then transferred into a reactive epoxy resin. After dissolution of PETg, the nanofillers remained oriented in the thermosetting matrix. The characterization of the obtained nanocomposites has been carried by means of different experimental techniques which provided complementary results.

Bioactive food-preserving systems are based on the use of a natural antimicrobial agent loaded in a carrier material, which is able to trigger its release once necessary and to control the rate of release, thereby exerting either lethal or inhibitory effects against food pathogens or spoilage microorganisms. In this study the Schiff base of chitosan was synthesized by the reaction with cinnamaldehyde at different concentrations. Cinnamaldehyde is an aromatic α,s-unsaturated aldehyde, and the major component in essential oils from some cinnamon species. It has been shown to exert antimicrobial activity against a wide range of microorganisms including bacteria, yeasts, and mould. The formation of the Schiff base is reversible under suitable conditions, and this might allow the release of the active cinnamaldehyde from chitosan, used as the carrier. The reaction kinetics was investigated by means of rheological analyses and infrared spectroscopy was used to assess the efficacy of the functionalization. Cinnamaldehyde-functionalized chitosan films were then prepared and tested antifungal properties in vitro. Moreover, the effect of the addition of expanded graphite sonicated stacks was evaluated in term of mechanical properties.

One of the key points for the successful development of nanocomposites is to obtain a good dispersion of the nanofillers in the polymer matrix. However, because of complex polymer-polymer and polymer-nanostructure interactions, the estimation of the dispersion is far from trivial. Dynamic rheological functions are mostly used to estimate the quality of dispersion. However, these rheological functions are sensitive to complex molecular architectures such as branching; thus, the accuracy of these rheological functions is limited for nanocomposites obtained using polymer matrices with these molecular architectures. Therefore, an estimation of the dispersion using other approaches needs to be explored. In this work, carbon nanotubes (CNTs) are firstly dispersed in a polyamide matrix by a low-frequency ultrasound-assisted extrusion process (kHz range). Then, high-frequency ultrasound wave propagation (MHz range) is used to estimate the dispersion of CNTs in polyamide matrices with different branching architectures. The quality of dispersion observed through the ultrasonic attenuation coefficient of the material matches with optical microscopy studies, in contrast with results obtained using dynamic rheological functions. Dynamic mechanical deformation induced by high-frequency ultrasound seems to be less sensitive to branching architectures, thus giving a better estimation of the quality of dispersion.

The need of reconstructing complex bone defects in the maxillo-facial region as a result of trauma, tumour surgery or congenital malformation has become a hot topic in the field of tissue engineering. Digital tools such as 3D CAD systems and rapid prototyping (RP) machines are a useful tool to realize custom made bone scaffolds. RP techniques allow the construction of complex physical models based on 3D clinical images elaborated by suitable software and CAD systems. Hydroxyapatite (HA) is one of the most used material for bone restoring because of its composition very closed to human bones and teeth. Producing a custom-made scaffold in a ceramic material directly by RP is therefore an exciting challenge. The aim of the present work was to investigate the potential of RP processes as a manufacturing method for products intended for personalized treatments by exploring the production of novel hydroxyapatite-based feedstock materials for RP purposes. Materials for two different kind of RP techniques were deeply characterized, evidencing that the presence of HA is able to greatly increase their physical, thermal and mechanical properties. Composites were subsequently used to obtain 3d structures by RP instruments.

This paper is aimed to study the suitability of poly(lactic acid) (PLA) for the production of biodegradable containers by rotational molding. To increase polymer toughness, PLA was plasticized with poly(ethylene glycole) (PEG), with an average molecular weight of 400 g/mol. Differential scanning calorimetry performed on neat PLA and PEG-plasticized PLA showed that the former is characterized by a better quenchability than the latter. Neat PLA and PEG-plasticized PLA were used for the production of rotational molding prototypes of simple shape. Owing to its very slow crystallization kinetics, a completely amorphous PLA was obtained by rotational molding with air cooling. As a consequence, rotomolded PLA is characterized by a good ductility and toughness. In contrast, the higher crystallization rate induced by the addition of PEG did not allow to obtain an amorphous structure for plasticized PLA, even if faster cooling was attained by water spraying. As a consequence, the PEG-plasticized PLA, characterized by a semicrystalline structure, shows a lower ductility and toughness compared to neat PLA.

This paper is aimed at studying the effect of the grade and the granulometry of poly(lactic acid) (PLA) on its processability by rotational molding. Two PLA grades were considered: a low melt flow rate (MFR), high viscosity, material, characterized by an excellent quenchability, leading to a completely amorphous structure of rotomolded samples; a high MFR, low viscosity, material, characterized by a lower quenchability, leading to a semicrystalline structure of rotomolded samples. Three different granulometries were considered: a coarser one, that is, the pellets as received, intermediate size pellets produced by extrusion followed by pelletizing, and a powder obtained by grinding of as received pellets. Besides the different dimensions, the intermediate size pellets also experienced a supplementary extrusion step, which induced some degradation in the material. For both grades and three granulometries, void-free prototypes were obtained, which indicate a very efficient sintering process, attributed to the low viscosity of all PLA grades. As a consequence, the modulus of the rotomolded samples was found to be unaffected by the PLA grade or granulometry. In contrast, the strength was shown to be more significantly dependent on quenchability than on the grade. To obtain an adequately high strength, an amorphous structure must be developed during cooling. Finally, the supplementary extrusion step experienced by the intermediate size pellets was shown to significantly decrease the strength of prototypes, as a consequence of the thermal degradation induced by this additional processing step.

Soft PVC is employed for the manufacturing of a wide range of products with different properties and a relatively low cost. The utilization of soft PVC is restricted by the poor thermal, chemical and mechanical resistance properties. Also, plasticizer migration can modify the properties or can make useless the materials for some applications because of toxicity or a general loss of properties. PVC crosslinking is the most effective way to improve mechanical and transport properties of rigid or flexible PVC at high temperatures, but at the same time the thermal stability of PVC may be significantly reduced. In this work, the crosslinking reaction of plasticized poly(vinyl chloride) (PVC) through difunctional amines was studied. The mechanisms involved in the crosslinking reaction were explained by Fourier transform infrared (FTIR) analysis. The thermal activated crosslinking reaction was studied by cone and plate rheometry, analyzing the evolution of viscoelastic properties of the suspension as a function of time and temperature. The effect of the addition of crosslinking agents on the thermal stability of the polymer was studied by thermogravimetric analysis (TGA), which revealed that crosslinking reactions promote thermal degradation phenomena in the polymer matrix. This is attributed to the formation of HCl and other species promoting polymer degradation during crosslinking, thus leading to higher weight loss during thermal treatment with respect to unmodified PVC plastisols. This was also confirmed by an evident yellowing after crosslinking, especially at higher temperatures.

In this work, the synthesis, formulation and characterization of a thermosetting resin based on cardanol, suitable as composite matrix, is presented. The polycondensation reaction between cardanol, a phenolic based by-product of the cashew nut industry, and formaldehyde in presence of a basic catalyst, in different molar ratios, has been applied to the synthesis of a resole type pre-polymer. A thermosetting resin, containing approximately 40% of cardanol by weight, has been obtained adding an epoxy monomer and an acid based catalyst to the resole compound. The reactivity of different functional groups of the mixture has been studied by FTIR (Fourier Transformed Infrared spectroscopy) while the calorimetric analysis has been applied to the definition of the curing cycle, also taking into account the mechanical performances of the matrix. The glass transition temperature ( T g ) of the resin, in the range 42–56 °C for different curing cycles and formulations, has been determined by dynamic-mechanical analysis. Finally, the formulation characterized by adequate properties and curing temperatures has been reinforced with short ramie, flax, hemp fibres, and with a juta fabric. For comparison purposes a standard polyester resin has been also used as matrix for the same juta fabric. In this last case, two different surface treatments of the fibre surface have been also attempted in order to improve the adhesion characteristics. Coupling natural fibres with a natural based matrix has led to an amount of natural components in the composite that can reach 73% by weight. Starting from the new cardanol based matrix and the above mentioned fibres, flat plane samples have been prepared and tested in tension and bending.

This paper reports on the development and the optimization of a thermoforming process (compression molding) for thermoplastic sandwich panels. The skins of the panels are fabricated from polypropylene (PP)/continuous glass fibers dry prepregs in the form of a commingled fabric. The use of two different types of core material has been used, a PP foam and a PP honeycomb. Additionally, two alternative methods for the thermoforming process have been analyzed, using either a one-stage or a two-stage process. In the one-step process, skin molding and skin-core bonding are carried out simultaneously. In the two-stage process, the skins are first thermoformed and then bonded to the core as the second stage. The influence of the selected process parameters on the mechanical properties of the panels has been experimentally investigated, leading to the identification of the preferred processing conditions. Polym. Compos. 25:307–318, 2004. © 2004 Society of Plastics Engineers.

The possibility to modulate cellulose-based hydrogel sorption properties through the insertion of molecular spacers between the crosslinks was investigated. Starting polymers were the sodium salt of carboxymethyl cellulose, a polyelectrolyte cellulose derivative, and hydroxyethyl cellulose, a nonpolyelectrolyte derivative. Poly(ethylene glycol) with various molecular weights was linked by its free ends at two divinyl sulfone (DVS) crosslinker molecules, to increase the average distance between two crosslinking sites and thus to act as a spacer. Both the effect of the concentration and the molecular weight of the spacer on the hydrogel final sorption properties in water and water solutions were investigated. The presence of the spacer allowed us also to perform hydrogel synthesis with higher concentrations of cellulose in the reactive mixture, and the effect of the polymer concentration in the batch was analyzed. Hydrogels obtained in the presence of spacers displayed significantly higher equilibrium sorption properties than those of the ones obtained without spacers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 168–174, 2003

A new procedure for the alignment of carbon nanotubes in a thermosetting matrix is proposed in this study. The two-step approach is based on (i) the alignment of carbon nanotubes (CNTs) in thermoplastic fibres by electrospinning and (ii) the transfer of these nanocompositefibres into a reactive thermosetting resin, in which they are easily soluble. After fibre dissolution, the CNTs remain aligned in the cured thermosetting matrix.The proof of concept is demonstrated by producing electrospunpolymethyl methacrylate (PMMA) fibres filled with single wall carbon nanotubes (SWCNTs) in the form of unidirectional tape, which are then solubilised into a vinylester (VE) matrix. The PMMA is easily dissolved by the styrene present in the VE resin, leaving SWCNTs aligned in the cured VE network, as confirmed by Raman spectroscopy studies. A 50% increase in elastic modulus (SWCNT 1.3. wt.%) has been obtained by dynamic mechanical analysis carried out in tensile mode at 1. Hz. Thanks to its ability to orient carbon nanotubes in a thermosetting matrix, the proposed method can be exploited also to transfer oriented nanofillers into continuous fibre composites, thus obtaining multiscale or hierarchical composites. © 2014 Elsevier Ltd.

Purpose The objective of this work was to develop composite hydrogels based on poly(ethylene glycol) diacrylate (PEGDA) and collagen (Coll), potentially useful for biomedical applications. Methods Semi-interpenetrating polymer networks (semi-IPNs) were obtained by photo-stabilizing aqueous solutions of PEGDA and acrylic acid (AA), in the presence of collagen. Further grafting of the collagen macromolecules to the PEGDA/poly(AA) network was achieved by means of a carbodiimide-mediated crosslinking reaction. The resulting hydrogels were characterized in terms of swelling capability, collagen content and mechanical properties. Results and Conclusions The grafting procedure was found to significantly improve the mechanical stability of the IPN hydrogels, due to the establishment of covalent bonding between the PEGDA/poly(AA) and the collagen networks. The suitability of the composite hydrogels to be processed by means of stereolithography (SLA) was also investigated, toward creating biomimetic constructs with complex shapes, which might be useful either as platforms for tissue engineering applications or as tissue mimicking phantoms.

This paper is aimed to study the suitability of bio-polymers, including poly-lactic acid (PLLA) and Mater-Bi, for the production of hollow components by rotational molding. In order to reduce the brittleness of PLLA, the material was mixed with two different plasticizers, bis-ethyl-hexyl-phthalate (DEHP) and poly-ethylene-glycol (PEG). The materials were characterized in terms of sinterability. To this purpose, thermomechanical (TMA) analysis was performed at different heating rates, in order to identify the endset temperatures of densification and the onset temperatures of degradation. Results obtained indicated that the materials are characterized by a very fast sintering process, occurring just above the melting temperature, and an adequately high onset of degradation. The difference between the onset of degradation and the endset of sintering, defined as the processing window of the polymer, is sufficiently wide, indicating that the polymers can be efficiently processed by rotational molding. Therefore, a laboratory scale apparatus was used for the production of PLLA and Mater-Bi prototypes. The materials were processed using very similar conditions to those used for LLDPE. The production of void-free samples of uniform wall thickness was considered as an indication of the potentiality of the process for the production of biodegradable containers.

The propagation of low intensity ultrasound in a curing resin, acting as a high frequency oscillatory excitation, has been recently proposed as an ultrasonic dynamic mechanical analysis (UDMA) for cure monitoring. The technique measures sound velocity and attenuation, which are very sensitive to changes in the viscoelastic characteristics of the curing resin, since the velocity is related to the resin storage modulus and density, while the attenuation is related to the energy dissipation and scattering in the curing resin. The paper reviews the results obtained by the authors’ research group in the last decade by means of in-house made ultrasonic set-ups for both contact and air-coupled ultrasonic experiments. The basics of the ultrasonic wave propagation in polymers and examples of measurements of the time-evolution of ultrasonic longitudinal modulus and chemical conversion of different thermosetting resins are presented. The effect of temperature on the cure kinetics, the comparison with rheological, low frequency dynamic mechanical and calorimetric results, and the correlation between ultrasonic modulus and crosslinking density will be also discussed. The paper highlights the reliability of ultrasonic wave propagation for monitoring the physical changes taking place during curing and the potential for online monitoring during polymer and polymer matrix composite processing.

In this work, a method developed for the measurement of the transversal permeability of fibrous reinforcement is presented. The permeability of a reinforcement is defined by the Darcy equation and can be obtained once the pressure drop through the reinforcement and the viscosity and average velocity of the fluid are known. The method used in this work is based on a proper modification of a capillary rheometer, obtained by substituting the capillary with a tool, capable of sustaining the reinforcement during reinforcement impregnation and through thickness flow. The developed device was used to measure the pressure built during the flow at different velocities of the rheometer piston. The impregnation tests were performed at different temperatures using a high-viscosity matrix characterized by a Newtonian behaviour. At each temperature, pressure versus velocity plots showed two distinct zones, each characterized by a different slope. The slope observed at low pressures was higher than the slope observed at pressures, suggesting an increase in the permeability with increasing pressure or velocity. The double slope was attributed to the existence of two different impregnation mechanisms, the first one being characteristic of the flow of the matrix around the reinforcement bundles and the second is the characteristic of the flow of the matrix inside each bundle. Dimensionless analysis models and scanning electron micrographs were used to support that the slope of the first portion of the plot is due to inter-bundle flow, whereas the slope of the second portion is due to global flow including both inter- and intra-bundle flow.

Coupled polymer/composite parts were obtained for adapting a bladder-molding technique previously developed for the production of hollow components with continuous fiber-reinforced thermoplastic matrix composites. The internal layer (bladder side) is made up of an unreinforced thermoplastic polymer, linear low-density polyethylene (LLDPE), and the external one (mold side) is made up of a thermoplastic matrix composite based on isotactic polypropylene (PP) and E-glass fabric. The adhesion between the two layers is achieved by applying pressure (

This review addresses thermoforming of thermoplastic matrix composites (TPCs) reinforced with long or continuous fibers and of sandwich panels obtained using TPCs as skins. Thermoforming is a very versatile class of processes, applied to the production of parts of different thickness, ranging from

The aim of this work is the analysis of ageing phenomenon occurring in amorphous thermoplastic polymers below their glass transition temperature by pressure-volume-temperature (PVT) analysis. The ageing behavior of different polymers as a function of the heating and cooling rates has been widespread studied. Also, different works in literature are aimed to study the effect of the applied pressure on the glass transition behavior. Another relevant aspect related to the glass transition behavior is related to the ageing effects, which can also be influenced by the applied pressure. This is a very relevant issue, since most of the polymers, during ageing, are subjected to mechanical loading. PVT analysis was used to study the ageing of amorphous PET copolymer (PETg) at different pressure levels. Specific volume-temperature curves measured during the cooling and the heating steps were used for calculating the relaxed specific volume, showing that ageing effects increase with increasing applied pressure. The evolution of the fictive temperature as a function of time was calculated from experimental data.

The fundamental concepts of dielectric behavior of polymers and the utilization of dielectric measurements for in situ monitoring of cure of polymers and composites are discussed. Information is presented on currently used dielectric sensors and the procedure for calculation of dielectric parameters from the monitored signal. The review is written to accommodate both the fundamental and the pragmatic aspects of dielectric monitoring of cure. In the final part of the review, a critical assessment is offered of the advantages and disadvantages of dielectric measurements for the in situ monitoring of processing of polymers and composites.

The effect of the presence of a hyperbranched OH-functionalized polymer (HBP) on the kinetics of cationic photopolymerization of an epoxy system was investigated employing two complementary techniques, photo-DSC and real-time FT-IR spectroscopy. Lower rates of cross-linking reactions and higher conversion degrees were obtained in photo-DSC experiments with respect to real-time FT-IR spectroscopy. A limited amount (10% wt) of HBP influenced to a certain extent the cure kinetics of the epoxy resin followed by RT-IR; a final conversion of epoxy groups equal to 100% was achieved by increasing the content up to 20% wt The addition of 10% wt of HBP leaves the cure kinetics of the CE resin studied by p-DSC almost unchanged. By increasing the HBP content, a slightly lower reaction rate is observed at lower reaction times. The presence of the HBP produced a continuous decrease of the Tg of the UV-cured epoxy resin but only modest reductions in its thermo-oxidative stability.

This work is focused on the preparation of new environmentally friendly hydrogels derived from cellulose and hence originating from renewable resources and characterized by biodegradable properties. Two cellulose derivatives, sodium carboxymethylcellulose (CMCNa) and hydroxyethylcellulose (HEC), were used for superabsorbent hydrogel preparation. Citric acid (CA), a crosslinking agent able to overcome toxicity and costs associated with other crosslinking reagents, was selected in a heat activated reaction. Differential scanning calorimeter (DSC), fourier transform infrared spectroscopy (FTIR), and swelling measurements were performed during the reaction progress to investigate the CA reactivity with each of the polymers. Also, CMCNa/HEC polymer mixtures (3/1 w/w) crosslinked with CA were investigated and compared with previous results. Finally, a possible reaction mechanism was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

The propagation of low-intensity ultrasound in polymers, acting as a high-frequency dynamic mechanical deformation, can be successfully used to monitor changes in the modulus of polymers associated with glass transition, crystallization, cross-linking, and other chemical and physical phenomena related to changes in the viscoelastic behavior, such as gelation phenomena. The velocity of sound is related to the polymer storage modulus and density, whereas the absorption of ultrasonic waves is related to the energy dissipation in the material and, therefore, to the loss modulus. Accordingly, ultrasonic measurements have been used by several authors to monitor the evolution of the viscoelastic moduli of polymers as a function of time or temperature and, recently, become a characterization technique of its own right, generally known as ultrasonic dynamic mechanical analysis (UDMA). Often the technique is used in conjunction with rheological methods as a means of providing a better insight into the viscoelastic behavior of polymer systems. As yet UDMA is underutilized primarily because of the low operating temperatures (usually below 100○C) of commercially available ultrasonic transducers, and also due to the requirement of a coupling medium to ensure an efficient energy transfer mechanism between the transducer and the test material. Despite these limitations, this paper shows that the use of ultrasonics is potentially a powerful method for the characterization of polymers, particularly as a tool for online monitoring of events occurring during polymer processing and in the manufacture of polymer matrix composites. The aim of this paper is to review the progress made in recent years, highlighting the potential and reliability of UDMA for monitoring physical transitions in polymers such as glass transition, melting, crystallization, as well as physical changes taking place during curing of thermosetting resins. © 2009 Wiley Periodicals, Inc. Adv Polym Techn 27:63–73, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20124

In this work nanocomposite adhesives obtained using an organically modified montmorillonite (OMM) in a polyurethane matrix were studied. An amount of organoclay ranging from 3% up to 18% by weight was added to the polyol resin before mixing with isocyanate. In particular, a typical adhesive formulation used in laminated films for food packaging was studied. The effect of different preparation procedures was compared in order to correlate exfoliation with rheological and mechanical properties. The basal distance of OMM before and after mixing with the polyol and after curing was characterized by X-ray diffraction. Composites with low content of OMM show an intercalated structure. A mix of exfoliated and intercalated layers was observed in the composites with the highest OMM content, before and after curing. The basal distance of OMM decreases after solvent mixing and curing, suggesting that exfoliation and intercalation are improved with respect to the uncured system. The viscosity of polyols-OMM systems was studied as function of shear rate in a cone-plate rheometer in order either to check the possible degradation of the polyol oligomer on to correlate the viscosity with the aggregation state of OMM. Viscoelastic properties of polyol oligomer were obtained by shear dynamic mechanical tests in the frequency range 0.1–16 rad/s. Finally the tensile properties of polyurethane clay-nanocomposites were measured.

In this preliminary work, a new process is examined for manufacturing hollow parts from continuous fiber-reinforced thermoplastic polymer. The new process combines the basic idea of bag forming (or bladder-assisted forming) with the rotation of the mold for the processing of thermoplastic matrix composites. A pressurized membrane is used to compact the composite on the inner wall of a mold, which is placed inside a forced convection oven. The mold is removed from the oven for the cooling stage. The process was initially developed by using a thermoplastic pre-preg obtained using yarns of commingled E-glass fibers with isotactic polypropylene (iPP). A preliminary characterization of the thermoplastic composite showed that the material can be consolidated with pressures as low as 0.01 MPa, which is readily achievable with the process of this study. The design of the mold and membrane was carried out on the basis of both structural analysis of the aluminum shell and thermal analysis of the mold. The mold thickness is of great importance with respect to both the maximum pressure allowed in the process and the overall cycle time. Molding was performed on stacks of three and six layers of yarn, varying the applied pressure between 0.01 and 0.05 MPa and maximum temperature of the internal air between 185°C and 215°C. The composite shells obtained under different processing conditions were characterized in terms of physical and mechanical properties. Mechanical properties comparable with those obtained by compression molding and vacuum bagging were obtained. The maximum values obtained are 12.1 GPa and 290 MPa for the flexural modulus and the flexural strength, respectively. Furthermore, the results obtained show that mechanical properties improve with increasing the pressure during the cycle and with the maximum temperature used in the process. © 2007 Wiley Periodicals, Inc. Adv Polym Techn 26:21–32, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20085

Air-coupled ultrasound in one-side transmission mode has been applied to monitor the curing process of an unsaturated polyester resin, commonly used as a matrix in glass reinforced composites. The evolution of the resin mechanical properties during cure has been measured from the variation of longitudinal velocity. The technique has demonstrated to be a very powerful tool for detecting the structural changes occurring at gelation and vitrification. The no-contact ultrasonic results have been compared with those obtained using conventional contact ultrasonic measurements, characterized by direct coupling between the transducer and the resin, and with the rheological measurements. The good agreement among the results of the different techniques demonstrates the reliability of air-coupled ultrasound in monitoring the changes of viscoelastic properties occurring during the cure of thermosetting polymers. A further advantage of the proposed one-side ultrasonic technique is the absence of physical contact between the transducers and the sample, which is relevant during composite manufacturing, where probe contact could adversely affect the part quality or access from both sides is not practicable. No-contact ultrasonic cure monitoring is suitable for both stationary and moving liquid or solid samples in several process conditions such as moulding, filament winding, etc., opening the way to new applications of ultrasound in the composite industry.

Peptide activated poly(ethylene glycol) (PEG)-based hydrogels have received wide attention as material for tissue engineering application. However, the close structure of these materials may pose severe barriers to tissue invasion and nutrient transport. The aim of this work was to synthesize highly interconnected macroporous PEG hydrogels, suitable for use as tissue engineering scaffolds, by combining the photocrosslinking reaction with a foaming process. In particular, various porous samples, differing for both the polymer molecular weight and concentration in the starting precursor solution, have been prepared and characterized by means of scanning electron microscopy and mercury porosimetry. Moreover, water swelling properties have been evaluated and compared with those of the conventional nonporous ones, by performing both equilibrium and kinetic swelling measurements in distilled water. Results indicated that foamed hydrogels display a well-interconnected porous network, suitable for tissue invasion and free molecular trafficking within them. Pores dimension as well as swelling rate can be modulated by polymer concentrations and bubbling agent composition in the precursor solution.

Peer-reviewed journal article, Applied Rheology

Hydrogels with good mechanical stability are generally obtained by chemical crosslinking. However, the compounds used as crosslinking agents are often highly toxic, and thus they are not recommended as starting materials in view of an environmentally safe production process and a biocompatible product. In this work chemically crosslinked superabsorbent hydrogels have been synthesized from water solutions of hydroxyethylcellulose (HEC), carboxymethylcellulose sodium salt (CMCNa) and hyaluronic acid (HA), using a non-toxic water-soluble carbodiimide (WSC) as crosslinking agent. Sorption capacity both in water and in water solutions at different ionic strength has been investigated, taking into account the effect of different chemical compositions. Moreover, uniaxial compression tests and dynamic-mechanical measurements on water swollen samples have been performed to probe the elastically effective degree of crosslinking of the polymeric network. In vivo tests on humans for the application of this material as a bulking agent in dietary regimes are in process and preliminary results are encouraging.

The aim of this study was to compare different models, either originating from literature or originally proposed in this study, for the interpretation of the melting behavior of polymers. In particular, these models, tested with a linear low-density polyethylene widely used in rotational molding, are suitable for coupling with energy balances in the study of polymer processing. We obtained the experimental data from differential scanning calorimetry (DSC) dynamic scans, assuming that the endothermic flux was related to the rate of melting of the polymer. The studied models were able to predict the broad melting temperature range typically observed during polymer melting with either a statistical or a kinetic approach. The two different approaches were compared with experimental DSC data. The analysis of model performances with complex thermal programs showed that the statistical approach could provide a more realistic representation of polymer melting. These models were particularly suitable in rotational molding, where the lack of any flow and, hence, of any crystalline orientation leads to a degree of melting determined by the actual temperature of the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 289–295, 2003