Polymer based nanocomposites: synthetic strategies for hybrid materials

Associating the well known advantages of hybrid materials to the wide potential of nanomaterials, the new and featuring class of polymer nanocomposites turned into one of the most intensively researched areas. This review highlights recent developments in the field of the synthesis of polymer based nanocomposites. Important issues related to the surface modification of fillers, in order to promote the compatibility between the inorganic/organic components, are also reported. The enhancement of the physical properties and the potential applications of polymer nanocomposites are considered in typical examples, given for each synthetic method describe

Enhanced compatibility between coconut fibers/PP via chemical modification for 3D printing

Aiming to produce high-quality bio-based 3D printed products, in this work, coconut fibers were chemical modified using caprolactone. Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic reasonance (NMR) confirmed the grafting of the hydroxyl groups present on the surface of the fibers with caprolactone units. Furthermore, from contact angle (CA) analyses, the higher hydrophobicity of fibers after chemical treatment was confirmed, which improved its affinity with PP. The enhanced filler/matrix compatibility was reflected on the mechanical performance and processability of the ensuing composites. The modified fibers derived composites showed higher stiffness and higher melting flow index (MFI), when compared to the untreated counterparts. The composites were used to produce 3D printed specimens. Smother filaments were obtained using modified fibers, which confirms the better compatibility of fibers/PP. The surface of the 3D printed composite specimen produced using treated fibers, presented smooth surface, similar to the PP. This observation highlights the enhancement of the 3D printing quality due to the chemical modification of fibers. © 2021, The Author(s), under exclusive licence to Springer Nature Switzerland AG.publishe

Enhancement of physical and reaction to fire properties of crude glycerol polyurethane foams filled with expanded graphite

The reation to fire of polyurethane foams (PUFs) has been a subject of increasing relevance, so in this study the reaction to fire performance of PUFs derived from crude glycerol (CG) has been improved using expanded graphite (EG). The influence of different loadings of EG on the physical–mechanical properties of composite foams has been assessed and the results obtained show that it has significant positive impact. Moreover, the reaction to fire of the PUF and EG/PUF composites has been investigated and the results obtained showed that the fire behavior of composite foams containing as little as 5 wt% of EG are significantly improved. Indeed a dramatic reduction of the rate of heat release, mass loss rate, effective heat of combustion and specific extinction area, has been observed even for a relative low amount of EG. Likewise, the use of Infrared Thermography as a function of time has proven that, when EG is used, the combustion stops suddenly and the temperature drops sharply compared with the behavior of the unfilled PUF sample, which suggests that EG acts like a flame extinguisher. The results obtained have proven the suitability of CG for the production of PUFs and that the addition of EG considerably improves the reaction to fire of composite foams.publishe

Development of structural layers PVC incorporating phase change materials for thermal energy storage

The use of poly(vinyl chloride) (PVC) structural layers incorporating phase change materials (PCM) for latent heat thermal energy storage (LHTES) has become more attractive in the recent years compared to other supporting materials. In this study, PVC layers with different types of PCM were prepared using blending and compression moulding methods. Two types of synthesized PCM, one based on paraffin and calcium carbonate (PCM@CaCO3) and the other on paraffin, silica and graphene oxide (PCM@SiGO) have been developed to enhance the thermal conductivity of the PVC matrix and thus achieve a more effective charging and discharging process. PVC layers prepared using a commercial PCM (PCM@BASF) were also prepared for comparison. SEM images and DSC results reveal homogeneous distribution of the PCM in PVC layers and that most PCM particles are undamaged. The shell material (in the case of PCM@BASF) and the shape stability (in the case of synthesized PCM@CaCO3 and PCM@SiGO) prevent leakage of molten paraffin during the PVC layer production. The thermal conductivity profile of the PVC layer without PCM have a decreasing tendency with the temperature increase when determined using different measurement approaches, the transient plane heat source method (HotDisk Analyser, TPS 2500 S) and thermal flux meter method (steady-state method). However, for PVC layers with PCM the thermal conductivity profile shows a different behaviour when the mean surface temperature of the specimen is below the phase change transition temperature range (increasing tendency). During phase change transition (18–26 °C), the thermal conductivity presents two distinct tendencies. Firstly, the thermal conductivity reveals a decreasing tendency as the mean temperature of the specimen rises and afterwards an increasing tendency. Secondly, when the mean surface temperature is above the phase change transition temperature range, the thermal conductivity profile shows a decreasing tendency, independent of the PCM. The mechanical properties of PVC layers were also assessed and the results obtained revealed that the incorporation of PCM into the PVC matrix reduces the mechanical performance of the composites, however for LHETS applications not subjected to high tensile stress levels (over 1 kPa), this is not a significant drawback.publishe

Understanding the interactions of imidazolium-based ionic liquids with cell membrane models

Cell membrane models have been used to evaluate the interactions of various imidazolium-based ionic liquids (ILs) with Langmuir monolayers of two types of phospholipids and cholesterol. Data from surface pressure isotherms, Brewster angle microscopy (BAM) and polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) pointed to significant effects on the monolayers of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and cholesterol, used to mimic the membranes of eukaryotic cells, for ILs containing more than 6 carbon atoms in the alkyl chain (i.e. n > 6). For ILs with less hydrophobic tails (n ≤ 6) and low concentrations, the effects were almost negligible, therefore, such ILs should not be toxic to eukaryotic cells. The hydrophobicity of the anion was also proved to be relevant, with larger impact from ILs containing tetrafluoroborate ([BF4]-) than chloride (Cl-). Molecular dynamics simulations for DPPC monolayers at the surface of aqueous solutions of alkylimidazolium chloride ([Cnmim]Cl) confirm the penetration of the IL cations with longer alkyl chains into the phospholid monolayer and provide information on their location and orientation within the monolayer. For monolayers of dipalmitoylphosphatidyl glycerol (DPPG), which is negatively charged like bacteria cell membranes, the ILs induced much larger effects. Similarly to the results for DPPC and cholesterol, effects increased with the number of carbon atoms in the alkyl chain and with a more hydrophobic anion [BF4]-. Overall, the approach used can provide relevant information of molecular-level interactions behind the toxicity mechanisms and support the design of (quantitative) structure-activity relationship models, which may help design more efficient and environmentally friendly ILs.publishe

Graphene oxide modified with PMMA via ATRP as a reinforcement filler

Graphene is a two-dimensional new allotrope of carbon, which is stimulating great curiosity due to its superior mechanical, electrical, thermal and optical properties. Particularly attractive is the availability of bulk quantities of graphene (G) which can be easily processed by chemical exfoliation, yielding graphene oxide (GO). The resultant oxygenated graphene sheets covered with hydroxyl, epoxy and carboxyl groups offer tremendous opportunities for further functionalization opening plenty of opportunities for the preparation of advanced composite materials. In this work poly(methyl methacrylate) (PMMA) chains have been grafted from the GO surface via atom transfer radical polymerization (ATRP), yielding a nanocomposite which was soluble in chloroform. The surface of the PMMA grafted GO (GPMMA) was characterized by AFM, HRTEM, Raman, FTIR and contact angle. The interest of these novel nanocomposites lies in their potential to be homogenously dispersed in polymeric dense matrices and to promote good interfacial adhesion, of particular relevance in stress transfer to the fillers. PMMA composite films were prepared using different percentages of GPMMA and pristine GO. Mechanical analysis of the resulting films showed that loadings as low as 1% (w/w) of GPMMA are effective reinforcing agents, yielding tougher films than pure PMMA films and even than composite films of PMMA prepared with GO. In fact, addition of 1% (w/w) of GPMMA fillers led to a significant improvement of the elongation at break, yielding a much more ductile and therefore tougher material. Thermal analysis showed an increase of the thermal stability properties of these films providing evidence that strong interfacial interactions between PMMA and GPMMA are achieved. In addition, AFM analysis, in friction force mode, is demonstrated to be an effective tool to analyse the surface filler distribution on polymer matrices

Phase change materials and carbon nanostructures for thermal energy storage: a literature review

The high thermal conductivity of carbon based nanostructures (CNs) has been recognized appropriate to be integrated into phase change materials (PCMs) to enhance the overall thermal properties of the obtained nanocomposites. The equilibrium of the possibility to enhance the thermal conductivity of the PCMs and the latent heat capcity are the key for their ability to store or dissipate a large amount of energy in a short period of time. This paper gives an update overview summarizing the state-of-the-art concerning nanocomposites prepared using PCMs and CNs with emphasis on the improvement of the latent heat capacity and of the thermal conductivity. Focus is directed towards experimental research studies regarding the enhancement of the thermal properties (thermal conductivity and the latent heat capacity) of PCMs obtained by the addition of the CNs by means of the encapsulation method. The majority of the reported research studies focus mainly on the thermal characterization of PCMs nanocomposites, however there is scarce information about the mechanisms explaining why/how the thermal properties are enhanced. This review outlines the results of the thermal conductivity and the latent heat capacity of PCMs/CNs nanocomposites, trying to identify the features that lead to the improvement of their thermal properties.publishe

Polymer encapsulation of CdE (E = S, Se) quantum dot ensembles via in-situ radical polymerization in miniemulsion

Cadmium sulfide and cadmium selenide/polymer nanocomposites were prepared via in-situ radical polymerization in a miniemulsion. Organically capped CdE (E = S, Se) quantum dots (QDs) were used as the starting materials and ensembles of these dots were encapsulated with no need of further surface treatment. The use of two polymer matrices was investigated: poly(styrene) (PS) and poly(n-butyl acrylate) (PBA). In both cases, homogenous nanocomposites were obtained and their optical properties were investigated by visible absorption and photoluminescence spectroscopy. Quantum size effects were assigned to the nanocomposites, indicating the integrity of the individual QDs upon polymer encapsulation using the miniemulsion process

Langmuir films from tailor-made semi-amphiphilic alternating (AB) heterocyclic copolymers

Alkyl-substituted polyheterocycles (cf. poly(3-alkylthiophene) and poly(N-alkylpyrrole)) do not form true monomol. films at the air-H2O interface, due to lack of the required hydrophobic-hydrophilic balance. The authors designed and synthesized 2 new semi-amphiphilic alternating (AB) heterocyclic copolymers via a Stille coupling route, to study their film forming properties at the air-H2O interface, as inferred through surface pressure-area isotherms and Brewster angle microscopy. The copolymers I and II possess a N-alkylpyrrole unit, alternated with phenylene and benzothiadiazole units, resp. While copolymer-I formed a stable multilayer stack, copolymer-II forms a monomol. monolayer, at the air-H2O interface. The Langmuir film of copolymer-II could also be transferred layer-by-layer onto a substrate by vertical dipping metho