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With the commitment to reducing environmental impact, bio-based and biodegradable aerogels may be one approach when looking for greener solutions with similar attributes to current foam-like materials. This study aimed to enhance the mechanical, thermal, and flame-retardant behavior of poly(vinyl alcohol) (PVA) aerogels by adding sodium alginate (SA) and tannic acid (TA). Aerogels were obtained by freeze-drying and post-ion crosslinking through calcium chloride (CaCl2) and boric acid (H3BO3) solutions. The incorporation of TA and SA enhanced the PVA aerogel’s mechanical properties, as shown by their high compressive specific moduli, reaching up to a six-fold increase after crosslinking and drying. The PVA/TA/SA aerogels presented a thermal conductivity of 0.043 to 0.046 W/m·K, while crosslinked ones showed higher values (0.049 to 0.060 W/m·K). Under TGA pyrolytic conditions, char layer formation reduced the thermal degradation rate of samples. After crosslinking, a seven-fold decrease in the thermal degradation rate was observed, confirming the high thermal stability of the formed foams. Regarding flammability, aerogels were tested through cone calorimetry. PVA/TA/SA aerogels showed a significant drop in the main parameters, such as the heat release rate (HRR) and the fire growth (FIGRA). The ion crosslinking resulted in a further reduction, confirming the improvement in the fire resistance of the modified compositions.

This work presents the experimental results of the mechanical and fracture behaviour of three polymeric blends prepared from two recycled plastics, namely polypropylene and opaque poly (ethylene terephthalate), where the second one acted as a reinforcement phase. The raw materials were two commercial degrees of recycled post-consumer waste, i.e., rPP and rPET-O. Sheets were manufactured by a semi-industrial extrusion-calendering process. The mechanical and fracture behaviours of manufactured sheets were analyzed via tensile tests and the essential work of fracture approach. SEM micrographics of cryofractured sheets revelated the development of in situ rPP/rPET-O microfibrillar composites when 30 wt.% of rPET-O was added. It was observed that the yield stress was not affected with the addition of rPET-O. However, the microfibrillar structure increased the Young’s modulus by more than a third compared with rPP, fulfilling the longitudinal value predicted by the additive rule of mixtures. Regarding the EWF analysis, the resistance to crack initiation was highly influenced by the resistance to its propagation owing to morphology-related instabilities during tearing. To analyze the initiation stage, a partition energy method was successfully applied by splitting the total work of fracture into two specific energetic contributions, namely initiation and propagation. The results revelated that the specific essential initiation-related work of fracture was mainly affected by rPET-O phase. Remarkably, its value was significantly improved by a factor of three with the microfibrillar structure of rPET-O phase. The results allowed the exploration of the potential ability of manufacturing in situ MFCs without a “precursor” morphology, providing an economical way to promote the recycling rate of PET-O, as this material is being discarded from current recycling processes.

Adding textures to surfaces is known to improve the external appearance of injection moulded components. However, when high surface quality is required, normally a paint coating is applied on top of the moulded textured surface. In this work, an alternative to painting for obtaining high quality surfaces is proposed, following an environmental-friendly process and having low production cost. Three different surface textures obtained by injection moulding have been characterized and compared with a painted one. Alternative topographical parameters such as the absolute functional height (AFH), the functional height distribution (FHD), texture slope (TS) or texture aperture angle (TAA) besides to the traditional roughness parameters such as the arithmetical mean height (Sa) and the root mean square height (Sq) have been utilized to characterize the random surface textures. The relationships between these parameters and the surface quality appearance represented by gloss and reflectivity contrast have been established using a new total appearance measurement (TAM) apparatus. It was found that by applying secondary operation on the textured mould cavity, such as adding micro roughness features or coatings, equal apparent quality to the ones obtained by painting can be reached.

Poly(lactic) acid, (PLA) is a biodegradable polymer that has attracted interest as a potential substitute for some thermoplastic polymers. However, its advanced brittleness at room temperature represents one of the major drawbacks for its general use. In this work, PLA was modified by reactive extrusion (PLAREx) to enhance the rheological behavior and to limit its degradation. The modified material was melt blended with ABS, analyzing the resultant morphology, rheological, thermo-mechanical and fracture behavior. Since PLA does not have reasonable compatibility with ABS, maleic anhydride-grafted ABS (ABS-g-Ma) was used as compatibilizer. The morphology of the PLAREx/ABS samples resulted in the formation of small ABS rods in the matrix. The presence of maleic anhydride contributed to reduce the interfacial energy of the blends and to obtain finer micro-domains of the ABS-rich phase in the PLAREx matrix. In the compatibilized blends, the presence of elongated ABS-rich phases opposed the free crack propagation and contributed to the increase in the fracture energy in comparison to neat PLA.

PLA bio-blends with a predominantly biosourced PA10.10 in the composition range 10-50wt.% were prepared by melt blending in order to overcome the advanced brittleness of PLA. Due to the inherent immiscibility of the blends, 30 wt.% of PA was needed to achieve a brittle-to-ductile transition and a co-continuous morphology was predicted at 58 wt.% of PA. The initial enhancement of the PLA rheological behaviour through the environmentally friendly reactive extrusion process yielded a finer and more homogeneous microstructure and hence enhanced the mechanical properties of the bio-blends at much lower PA contents. The brittle-to-ductile transition could be achieved with only 10 wt.% and co-continuity was observed already at 44 wt.% of PA. Results indicate the significant potential of modifying PLA flow behaviour as a promising green manufacturing method toward expanding PLA-based bio-blends applications.

Square plates (nominal thickness: 3 mm, nominal width: 100 mm) of different rheologically modified PLA/ABS blends were manufactured through injection molding, with or without adding ABS grafted with maleic anhydride (MAH). During processing, the properties of the melt were stabilized and enhanced by the addition of a styrene-acrylic multi-functional-epoxide oligomeric reactive agent (SAmfE). PLA-REX was obtained by reactive extrusion of PLA. A general analytical equation was used in order to evaluate the kinetic parameters of the thermal degradation of PLA−REX/ABS and PLA−REX/ABS/ABS−g−MAH blends through thermogravimetric analysis. The thermal degradation of these blends occurred through two different reaction steps. Various empirical and theoretical solid-state mechanisms were tested to elucidate the best kinetic model. In order to reach this goal, plots of standardized conversion functions were constructed. Given that it is not always easy to visualize the best accordance between experimental and theoretical values of standardized conversion functions, a recently proposed index was determined to quantitatively identify the best mechanism. By doing that, it has been possible to determine the right activation energy of the thermal degradation. It has been demonstrated that the best mechanisms for these materials were R2 (i.e. phase-boundary-controlled reaction (contracting area)) for the first step (α 70%). The thermal stability of PLA−REX/ABS blend was greatly improved by adding the ABS−g−MAH compatibilizer. These findings were also confirmed by means of morphological characterization through scanning electron microscopy.

A series of low density, highly porous clay/poly(vinyl alcohol) composite aerogels, incorporating ammonium alginate, were fabricated via a convenient and eco-friendly freeze drying method. It is significant to understand rheological properties of precursor gels because they directly affect the form of aerogels and their processing behaviors. The introduction of ammonium alginate impacted the rheological properties of colloidal gels and improved the mechanical performance of the subject aerogels. The specific compositions and processing conditions applied to those colloidal gel systems brought about different aerogel morphologies, which in turn translated into the observed mechanical properties. The bridge between gel rheologies and aerogel structures are established in the present work.

In this work, microcellular ABS foams were studied. A series of injection molding samples defined by a design of experiments was carried out to analyze the effect of shot volume, mold temperature, and injection velocity on the morphology, mechanical properties, and surface roughness of microcellular samples. A predominant influence of shot volume on the cell structure and tensile properties was evidenced. Higher cell densities and narrower cell size distributions were obtained at lower injection volume. However, elastic modulus and tensile strength were improved by increasing the shot size. The effect of mold temperature and injection velocity was secondary. Higher levels of mold temperature and injection rate provided finer cell morphologies, but their effects on the elastic modulus and tensile strength were negligible. The decrease in shot volume and increase in gas content led to poor surface quality, whereas it was greatly improved by raising both mold temperature and injection velocity

A facile cross-linking strategy to construct flame retardant cellulose nanofibril (CNF)/sodium montmorillonite (MMT) aerogels with improved mechanical properties, by incorporating melamine-formaldehyde (MF) resins into precursor suspensions followed by a freeze-drying process, is reported in this work. Scanning electron microscopy images indicate that MF cross-linking does not significantly change the microstructures of CNF and CNF/MMT aerogels. However, the cross-linking improves the materials’ mechanical and flame properties. By incorporating 50 wt% of MF, the compression moduli and compressive stress of CNF aerogels increase by 316% and 114%, respectively. The limiting oxygen index (LOI) value of CNF aerogels also increases from 17.1% to 23.4%. Further addition of MMT increases the CNF aerogels’ LOI value to 57% and increases the maximum decomposition temperature by nearly 20 °C. This occurs because MMT and MF induce a synergistic effect which improves the flame retardant properties of the CNFs aerogels. In CNF/MMT composite aerogels, the introduction of 34 wt% of MF leads to a 54.6% reduction of the peak of heat release rate and a 53.2% decrease in total heat release. CNF aerogels made from sustainable feedstocks with excellent mechanical properties and high flame retardancy, like those discussed herein, show promise as fire resistant biofoams

Square plates (nominal tickness: 3 mm, nominal width: 100 mm) of diferent rheolgically modified PLA/acrylonitrile-butadiene-styrene (ABS) blends were manufactured through injection molding process. During processing, the properties of the melt were stabilized and enhanced by the addition of a styrene-acrylic multi-functional-epoxide oligomeric reactive agent (SAmfE). The general analytical equation has been used in order to evaluate the kinetic parameters of the thermal degradation of PLA-REX, ABS and its bioblend with a weight content of 70/30. Various empirical and theoretical solid-state mechanisms have been tested to elucidate the best kinetic model. In order to reach this goal, activation energy values were calculated by means of the Kissinger–Akahira–Sunose method. On the other hand, the standardized conversion functions have been constructed. Given that it is not always easy to visualize the best accordance between experimental and theoretical values of standardized conversion functions, a recently proposed index has been determined to quantitatively support our findings relative to the best reaction mechanisms. It has been demonstrated that the best mechanism for the thermal degradation of PLA-REX and ABS was the random scission of macromolecular chains. The bioblend thermal degradation occurred in two steps: the first step (α < 60%) took place through an R2 mechanism whereas the second step (α > 75%) did it according an F3 mechanism. Moreover, y(α) master plots have also been used in order to confirm that the selected reaction mechanisms were adequate The Ministry of Economy and Competitiveness projects MAT2013-40730-P and MAT2016-80045-R (AEI/FEDER, UE) of the Spanish Government financially supported this work

Electronic version of an article published as "Express polymer letters" vol. 7, nº. 2, February 2013, p. 172-185. Cyclic butylene terephthalate oligomers (CBT) were reacted in a ring-opening polymerization with three types of isocyanates: a bifunctional aromatic type, a bifunctional aliphatic type and a polymeric aromatic isocyanate. All reactions took place in a batch mixer. The use of 0.5 to 1 wt% isocyanate led to a dramatic increase in elongation at break of polymerized cyclic butylene terephthalate (pCBT), from 8 to above 100%. The stiffness and strength of the modified pCBT, however, were found to slightly decrease. Proton nuclear magnetic resonance (NMR) analysis shows that the formation of thermally stable amide groups is the dominant chain extension reaction mechanism. Gel content measurements suggest a linear structure for samples containing bifunctional isocyanates while pCBT modified with polyfunctional isocyanate exhibited some gel formation at higher isocyanate content. Melting and crystallization temperatures as well as degree of crystallinity were found to decrease with increasing isocyanate content. No phase separation was detected by scanning electron microscopy (SEM) analysis. Moreover, a high degree of polymerization is deduced due to the absence of CBT oligomer crystals.

A unique set of double-edge notched tension specimens of a Polyethylene Terephthalate Glycol-modi¿ed ¿lm was tested in mode I, plane stress. The load was registered on a universal testing machine. The displacements, ligament lengths, and video frames were recorded by a Digital Image Correlation system. With these registered data, the essential work of fracture, J-integral, and crack tip opening displacement (CTOD) fracture concepts have been applied. The onset of crack initiation was through a complete yielded ligament. The analysis showed that the intrinsic speci¿c work of fracture, we, is the speci¿c energy just up to crack initiation, which is an initiation value. we has both a coincident value and the same con-ceptual meaning as Jo, the J-integral at the onset of crack initiation. The relationship between Jo and CTOD is also determined. The in¿uence on the notch quality when the specimens were sharpened by two different procedures, femtosecond laser ablation and razor blade sliding, was analysed in detail.

Cyclic butylene terephthalate (CBT) was polymerized in the presence of a low molecular weight bifunctional epoxy resin. The resultant chain extended polymerized CBT (pCBT) showed an increased ductility compared to that of conventionally polymerized pCBT for all analyzed epoxy concentrations (1–4 wt.%). The best results were obtained with 2 wt.% of epoxy resin. Other mechanical properties remained relatively unaffected by the epoxy resin. 1 H NMR analysis suggested an esterification reaction of the carboxyl end groups of pCBT and the glycidyl functional groups of the diepoxide. With increasing epoxy content, the chain extended pCBT showed an increasing molecular weight and a decreasing glass transition. Crystallization and melting temperatures as well as crystallinity also decreased with increasing epoxy concentration.

In this study, the morphology and thermo-mechanical behavior of composites formed by a polyoxymethylene (POM) matrix and monosilanolisobutyl polyhedral oligomeric silsesquioxane (msib-POSS) filler have been studied. The msib- POSS molecules were added to the POM by direct melt blending at loadings between 0 and 10 wt.%. Hydrogen bonding interactions were detected between POM and msib-POSS Si–OH groups, increasing their mutual compatibility and leading to nanometer-size dispersion of some msib-POSS molecules. These interactions do not prevent POSS aggregation during blending, but lead to micron-scale msib-POSS domains. The thermal decomposition temperature of the composites remained practically constant under inert and oxidative conditions. The low temperature thermal transition (g) and glass transition temperature (Tg) of POM were found to move to higher temperatures only when 2.5 wt.% of msib-POSS was added, indicating that POSS is physically linked to the POM chains, restricting their motion under those conditions. Low content (2.5 wt.%) of msib-POSS results in antiplastization, whereas higher levels of POSS lead to a decrease in the storage modulus of the polymer. The relationships among these effects and the morphological characteristics of the systems will be discussed herein

The influence of the functionalization of fully condensed POSS cages on the properties of POMbased nanocomposites is studied. POSS with different organic substituents [glycidylethyl, aminopropylisobutyl, and poly(ethylene glycol)] are taken into account and melt mixed with POM. Good dispersion was achieved upon the addition of amino functionalized POSS, leading to an increase on the thermal decomposition temperature under nitrogen atmosphere up to 50 8C. However, mm-size aggregates were observed for other nanocomposites. There is no significant change in other thermal properties of the nanocomposites. The relationships among these effects and the morphological characteristics of the systems were analyzed.

Ethylene–(vinyl alcohol) (EVOH)/organo-modified montmorillonite clay (OMMT) composites were prepared using commercial OMMTs with two different organo-modifiers. The first one has polar groups, which interact with EVOH chains, whereas the second one is non-polar. Composites with a high weight percentage of OMMT were prepared by melt-extrusion in a twin-screw extruder. Films were prepared in a cast-film line in order to evaluate the tensile and fracture parameters. The morphology of the EVOH/OMMT composites was characterized using wide-angle X-ray scattering and transmission electron microscopy, complemented by image analysis. The mechanical properties were evaluated using uniaxial tensile tests; the fracture behaviour was analysed using the essential work of fracture (EWF) method. Results show differences in composite morphologies and crystalline fraction, depending on the content and the nature of the organo-modifier. The mechanical and fracture behaviours are strongly influenced by those parameters, which act in opposite senses. The EWF method is shown to be a useful tool for the analysis of the structure–properties relationships of these composites. Copyright © 2010 Society of Chemical Industry

BACKGROUND: Ethylene–(vinyl alcohol) (EVOH) copolymer/organo-modified montmorillonite (OMMT) composites were investigated. Composites with two different percentages by weight of OMMT were prepared using a melt-extrusion procedure in a twin-screw extruder, using EVOH as matrix. Films made of EVOH and EVOH/OMMT composites were prepared in a cast-film extrusion line. RESULTS: The mechanical properties were evaluated by tensile tests and the fracture behaviour was analysed using the essential-work-of-fracture (EWF) method. Fracture characterization was carried out for the two main processing directions: melt flow direction and transverse direction. Fractographic observations were made using scanning electron microscopy. CONCLUSION: The tensile test results indicated good compatibility between EVOH and OMMT. In addition, the fracture tests showed the influence of the clay particle arrangement on the fracture behaviour, showing an increase in the specific essential work of fracture, we, which was attributed to the EVOH–OMMT interaction. The plastic term, βwp, showed different trends depending on the test direction, explained by the size of the plastic zone and the restrictions to the EVOH plastic flow promoted by the clay particles. In this sense, the EWF method is shown to be a very useful tool for the analysis of structure–property relationships in polymer–organo-clay composites. Copyright © 2009 Society of Chemical Industry

In this work, the morphology and thermo-mechanical behaviour of nanocomposites formed by a polycarbonate (PC) matrix and polyhedral oligomeric silsesquioxane with phenethyl substituents (Ph-POSS) have been studied. The Ph-POSS nanocages were added to the PC by direct melt blending at loadings between 0% and 15 wt%. Good dispersion was achieved up to 5 wt% of nanofiller. At higher loadings micron-sized aggregates were observed in the nanocomposites by scanning and transmission electron microscopy. Increasing of Ph-POSS content lead to phase separation, agglomeration and low values on the final properties. The DSC and DMA analyses showed that increasing the amount of nanocages caused a continuous decrease on the composite’s Tg. Although little increments on the polycarbonate decomposition temperature were found, the presence of Ph-POSS did not improve significantly the thermal stability. Under nitrogen atmosphere the degradation mechanism of PC was not affected by the POSS. The residual weights obtained under oxygen atmosphere were in agreement with the theoretical weights of the Ph-POSS added. With respect to the nanocomposites mechanical properties the most remarkable trend was an improvement on the composite’s yield stress having the maximum at 5 wt% of nanofiller. Higher amounts of Ph-POSS lead to a decrease on the yield stress, finding even lower values than the one corresponding to the neat matrix. This behaviour has been attributed to the presence of large POSS agglomerates with low adhesion to the polymer matrix. A continuous decrease on the strain at break was also observed, reflecting the brittle character of the formed composites.

One of the most important features when predicting the impact response of plastic components is the characterisation of the material in impact conditions. In this work, a new method to obtain stress/strain curves of thermoplastics at constant strain-rates is proposed. Instrumented tensile-impact tests have been performed on polypropylene samples at different impact energies. The use of tensile-impact techniques avoids some problems associated with flexural impact tests, and permits to determine the stress/strain curves and the strain-rate dependence of thermoplastics' behaviour in impact conditions. The results show that in the range of strain-rates analysed, polypropylene has an elastic–plastic behaviour with a slight plastic strain hardening. The isostrain-rate stress/strain curves can be used as material data in finite element simulations of impact events.

A natural bentonite rich in calcium montmorillonite (CaMMT) was initially purified and ion-exchanged to obtain sodium montmorillonite (NaMMT). Both clays were organophillised by cationic exchange reaction with undecyl-ammonium chloride, and characterized. Isotactic poly(propylene) (PP) was melt-compounded with both the unmodified and the organophilic montmorillonites. The hybrids produced have been characterized structurally, thermally and mechanically. Maleic anhydride-grafted PP (MAH-g-PP) was used as compatibilizer in some of the formulations. Homologous series of hybrids were also synthesized employing blends of PP/PET and compared with those of the pure PP to investigate possible beneficial effects due to the presence of small amounts of PET on the microstructure and properties of this kind of materials. The analysis of the results indicates some extension of both macromolecules intercalation and clay particles exfoliation in the hybrids prepared with the organophilic montmorillonite. The hybrids prepared with compatibilized PET/PP blends were found to have a better nanostructure.

The influence of processing induced morphology, thickness and ethylene content (EC) of different ethylene–propylene block copolymers on fracture properties has been studied using the essential work of fracture (EWF) method. To analyse the influence of EC, four different materials were chosen with 0, 5.5, 7.8, and 8.4% in weight EC. Each material was injected in three different thicknesses (1, 2 and 3 mm). The resulting plaques were tested using the EWF method in both main orientations; the melt flow direction and transverse to melt flow direction. Different fracture behaviours have been observed, some of them preventing the applicability of the EWF method. Polarised light microscopy observations have revealed the existence of a skin/core structure, which is reduced with an increase in thickness and EC.

Cyclic butylene terephthalate (CBT (R)) is an interesting matrix material for the preparation of nanocomposites due to its very low, water-like melt viscosity which favours clay exfoliation. Nevertheless, polymerized CBT (pCBT) is inherently brittle. This paper reports the preparation of isocyanate-toughened nanocomposites made from CBT and organo-modified montmorillonite. The role of the organoclay as reinforcement and the polymeric isocyanate (PMDI) as toughening agent on the properties of pCBT was studied. The organoclay increased the stiffness and strength by up to 20% whereas the PMDI improved the deformation behaviour. However, the PMDI did not affect the degree of clay dispersion or exfoliation and flocculated-intercalated structures were observed. The compatibility between the pCBT matrix and clay was further increased by preparing PMDI-tethered intercalated organoclay. The modified organoclay then exfoliated during ring-opening polymerization and yielded true pCBT/clay nanocomposites. This work demonstrates that reactive chain extension of CBT with a polyfunctional isocyanate is an effective method to obtain toughened pCBT nanocomposites. Moreover, isocyanates can enhance the compatibility between pCBT and nanofiller as well as the degree of exfoliation.

Low flammability, foam-like materials based on bio-based, renewable ammonium alginate and sodium montmorillonite clay were fabricated through a simple, environmentally-friendly freeze-drying process in which water is used as solvent. These materials exhibit mechanical properties similar to those of rigid PU foams or balsa; the compressive modulus (1–97 MPa) and density (0.047–0.174 g/cm3) increase with increasing solids content, with an associated change from a layered to network microstructure structure. Calcium ions, either added directly or indirectly via CaCO3/gluconolactone (GDL) are an effective crosslinking agent for alginate, with the GDL route providing the greatest enhancement of mechanical properties. The thermal stability of the aerogels is also enhanced by the presence of crosslinking. The alginate/clay aerogels possess inherently low flammability, as measured by cone calorimetry, with heat release values decreasing as the proportion of clay in the composites is increased.