Study of the Crystal Structure and Hydrogen Bonding during Cold Crystallization of Poly(trimethylene 2,5-furandicarboxylate).

Here, we present a detailed description of the in situ isothermal crystallization of poly(trimethylene 2,5-furandicarboxylate)(PTF) as revealed by real-time Fourier transform infrared spectroscopy (FTIR) and grazing incidence wide-angle X-ray scattering (GIWAXS). From FTIR experiments, the evolution of hydrogen bonding with crystallization time can be monitored in real time, while from GIWAXS, crystal formation can be followed. Density functional theory (DFT) calculations have been used to simulate FTIR spectra for different theoretical structures, enabling a precise band assignment. In addition, based on DFT ab initio calculations, the influence of hydrogen bonding on the evolution with crystallization time can be understood. Moreover, from DFT calculations and comparison with both FTIR and GIWAXS experiments, a crystalline structure of poly(trimethylene 2,5-furandicarboxylate) is proposed. Our results demonstrate that hydrogen bonding is present in both the crystalline and the amorphous phases and its rearrangement can be considered as a significant driving force for crystallization of poly(alkylene 2,5-furanoate)s.

The Mechanical, Thermal, and Biological Properties of Materials Intended for Dental Implants: A Comparison of Three Types of Poly(aryl-ether-ketones) (PEEK and PEKK).

Regarding the dynamic development of 3D printing technology, as well as its application in a growing part of industries, i.e., in the automotive industry, construction industry, medical industry, etc., there is a notable opportunity for its application in producing dental implants, which presents a promising alternative to traditional implant manufacturing methods. The medical industry is very restrictive regarding the applied materials, and it is necessary to use materials that exhibit very good mechanical and thermal parameters, show clinical indifference and biocompatibility, are non-allergenic and non-cancerous, and are likely to sterilize. Such materials are poly(aryl-ether-ketone)s (PAEK)s, mainly poly(ether-ether-ketone) (PEEK) and poly(ether-ketone-ketone) (PEKK), that are found to be high-performance polymers and can be defined as materials that retain their functionality even in extreme conditions. In the present paper, two types of PEEKs and PEKK were compared regarding their structural, mechanical, and thermal properties along with the biological activity toward selected strains. The tested samples were obtained with Fused Deposition Modeling (FDM) technology. The PEKK, after heat treatment, exhibits the most promising mechanical properties as well as less bacterial adhesion on its surface when compared to both PEEKs. Consequently, among the evaluated materials, PEKK after heat treatment stands out as the optimal selection for a dental prosthesis.

Supramolecular structure, relaxation behavior and free volume of bio-based poly(butylene 2,5-furandicarboxylate)-block-poly(caprolactone) copolyesters.

In the present study, a fully plant-based sustainable copolyester series, namely poly(butylene 2,5-furandicarboxylate)-block-poly(caprolactone)s (PBF-block-PCL)s were successfully synthesized by melt polycondensation combining butylene 2,5-furandicarboxylate with polycaprolactone diol (PCL) at different weight ratios. Differential scanning calorimetry (DSC) showed that only PBF underwent melting, crystallization from the melt, and cold crystallization. Thermogravimetric analysis (TGA) revealed outstanding thermal stability, exceeding 305 °C, with further improvement in thermal and thermo-oxidative stability with increasing PCL content. Broadband dielectric spectroscopy (BDS) revealed that at low temperatures, below the glass transition (Tg) all copolyesters exhibited two relaxation processes (ß1 and ß2), whereas the homopolymer PBF exhibited a single ß-relaxation, which is associated with local dynamics of the different chemical bonds present in the polymer chain. Additionally, it was proved that an increase in PCL content affected the dynamics of the chain making it more flexible, thus providing an increase in the value of the room temperature free volume fractions (fv) and the value of elongation at break. These effects are accompanied by a decrease in hardness, Young's modulus, and tensile strength. The described synthesis enables a facile approach to obtain novel fully multiblock biobased copolyesters based on PBF and PCL polyesters with potential industrial implementation capabilities.

Polymer Hybrid Nanocomposites Based on Homo and Copolymer Xlpe Containing Mineral Nanofillers with Improved Functional Properties Intended for Insulation of Submarine Cables.

Cross-linked polyethylene (XLPE) is one of the most popular insulation materials used in the production of medium and high voltage cables (MV, HV). This article presents the results of research carried out on two types of commercially used insulation materials, modified with the addition of organophilic phyllosilicate (CLOISITE C20A)and halloysite nanotubes (HNTs). The influence of fillers on the mechanical properties of insulating materials is discussed as a potential mechanism for increasing their resistance to the phenomenon of water-tree. SEM and XRD analyses were performed to investigate the morphology and DSC for comparing phase transitions. Mechanical and functional properties for different concentrations of nanofillers, such as their hybrids, were also investigated.

Relaxation Dynamics of Biomass-Derived Copolymers With Promising Gas-Barrier Properties.

This article presents an experimental study on the relaxation dynamics of a series of random copolymers based on bio-friendly comonomers with interesting gas barrier properties. We analyze the relaxation response in the glassy and ultraviscous regime of poly (trimethylene furanoate/sebacate) random copolymers via dielectric spectroscopy. We report lower values of dynamic fragility [a dimensionless index introduced in 1985 (Angell, Relaxations in Complex Systems, 1985)] in comparison to popular polyesters widely used in industry, such as poly (ethylene terephthalate), suggesting that the amorphous phase of these furanoate-based polyesters adopt an efficient chain packing. This is consistent with their low permeability to gases. We also discuss on different equations (phenomenological and theory-based approaches) for fitting the temperature-evolution of the alpha relaxation time.

The Properties of Poly(ester amide)s Based on Dimethyl 2,5-Furanedicarboxylate as a Function of Methylene Sequence Length in Polymer Backbone.

A series of poly(ester amide)s based on dimethyl furan 2,5-dicarboxylate (DMFDC), 1,3-propanediol (PDO), 1,6-hexylene glycol (HDO), and 1,3-diaminopropane (DAP) were synthesized via two-step melt polycondensation. The phase transition temperatures and structure of the polymers were studied by differential scanning calorimetry (DSC). The positron annihilation lifetime spectroscopy (PALS) measurement was carried out to investigate the free volume. In addition, the mechanical properties of two series of poly(ester amide)s were analyzed. The increase in the number of methylene groups in the polymer backbone resulted in a decrease in the values of the transition temperatures. Depending on the number of methylene groups and the content of the poly(propylene furanamide) (PPAF), both semi-crystalline and amorphous copolymers were obtained. The free volume value increased with a greater number of methylene groups in the polymer backbone. Moreover, with a lower number of methylene groups, the value of the Young modulus and stress at break increased.

Influence of Rigid Segment Type on Copoly(ether-ester) Properties.

The growing ecological awareness of society created the tendency to replace petrochemically based materials with alternative energy carriers and renewable raw materials. One of the most requested groups of polymer materials with significant technological importance is thermoplastic elastomers (TPE). They combine the properties of elastomers such as flexibility with the typical properties of thermoplastics, like easy processing. Herein, one compares the influence of rigid segments on the properties of copoly(ester-ether). Thermoplastic polyesters based on bio-1,6-hexanediol and terephthalic (T), furanic (F), and napthalate (N) diesters, i.e., PHT, PHF, and PHN, were obtained employing melt polycondensation. Additionally, to grant elastic properties of polyesters, systems containing 50 wt.% of bio-based polyTHF®1000 (pTHF) with a molecular mass of 1000 g/mol, have been prepared. The composition and chemical structure have been determined by 1H nuclear magnetic resonance (NMR) and Fourier transformed infrared spectroscopy (FTIR) analyses. The temperatures corresponding to phase transition changes were characterized by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) analyses. The crystalline structure was examined by X-ray diffraction (XRD) analysis. Additionally, the influence of pTHF-rich segment on the tensile properties, water absorption, as well as thermal and thermo-oxidative stability, has been analyzed. It was found that incorporation of soft phase allows creation of thermoplastic elastomers with tensile characteristics comparable to the commercially available ones, by means of elongation at break higher than 500%, low values of tensile modulus, without exhibiting yield point.

Halloysite Nanotubes and Silane-Treated Alumina Trihydrate Hybrid Flame Retardant System for High-Performance Cable Insulation.

The effect of the presence of halloysite nanotubes (HNTs) and silane-treated alumina trihydrate (ATH-sil) nanofillers on the mechanical, thermal, and flame retardancy properties of ethylene-vinyl acetate (EVA) copolymer/low-density polyethylene (LDPE) blends was investigated. Different weight percentages of HNT and ATH-sil nanoparticles, as well as the hybrid system of those nanofillers, were melt mixed with the polymer blend (reference sample) using a twin-screw extruder. The morphology of the nanoparticles and polymer compositions was studied using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The mechanical properties, hardness, water absorption, and melt flow index (MFI) of the compositions were assessed. The tensile strength increases as a function of the amount of HNT nanofiller; however, the elongation at break decreases. In the case of the hybrid system of nanofillers, the compositions showed superior mechanical properties. The thermal properties of the reference sample and those of the corresponding sample with nanofiller blends were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Two peaks were observed in the melting and crystallization temperatures. This shows that the EVA/LDPE is an immiscible polymer blend. The thermal stability of the blends was improved by the presence of HNTs and ATH-sil nanoparticles. Thermal degradation temperatures were shifted to higher values by the presence of hybrid nanofillers. Finally, the flammability of the compositions was assessed. Flammability as reflected by the limiting oxygen index (OI) was increased by the presence of HNT and ATH-sil nanofiller and a hybrid system of the nanoparticles.

Biobased Thermoplastic Elastomers: Structure-Property Relationship of Poly(hexamethylene 2,5-furanodicarboxylate)-Block-Poly(tetrahydrofuran) Copolymers Prepared by Melt Polycondensation.

A series of poly(hexamethylene 2,5-furanodicarboxylate)-block-poly(tetrahydrofuran) (PHF-b-F-pTHF) copolymers were synthesized using a two-stage procedure, employing transesterification and polycondensation. The content of pTHF flexible segments varied from 25 to 75 wt.%. 1H nuclear magnetic resonance (NMR) and Fourier transformed infrared spectroscopy (FTIR) analyses were applied to confirm the molecular structure of the materials. Differential scanning calorimetry (DSC), dynamic mechanical measurements (DMTA), and X-ray diffraction (XRD) allowed characterizing the supramolecular structure of the synthesized copolymers. SEM analysis was applied to show the differences in the block copolymers' morphologies concerning their chemical structure. The influence of the number of flexible segments in the copolymers on the phase transition temperatures, thermal properties, as well as the thermo-oxidative and thermal stability was analyzed. TGA analysis, along with tensile tests (static and cyclic), confirmed the utilitarian performance of the synthesized bio-based materials. It was found that an increase in the amount of pTHF caused the increase of both number-average and weight-average molecular weights and intrinsic viscosities, and at the same time causing the shift of the values of phase transition temperatures toward lower ones. Besides, PHF-b-F-pTHF containing 75 wt.% of F-pTHF units was proved to be a promising thermoplastic shape memory polymer (SMP) with a switching temperature of 20 °C.

Effect of Halloysite Nanotube on Mechanical Properties, Thermal Stability and Morphology of Polypropylene and Polypropylene/Short Kenaf Fibers Hybrid Biocomposites.

In this article, the effect of the addition of halloysite nanotube (HNT) on the mechanical and thermal stability of polypropylene (PP) and PP/kenaf fiber biocomposites has been investigated. Different volume contents of HNTs ranging from 1 to 10 vol.% were melt mixed with PP and PP/kenaf fibers. The volume content of kenaf fibers was kept constant at 30%. The morphology of HNTs within the PP matrix has been studied via scanning electron microscopy (SEM). The morphological results revealed that HNT was uniformly dispersed in the PP matrix already at a low concentration of 1 and 2 vol.%. The mechanical properties of the manufactured nanocomposites and hybrid biocomposites such as Young's modulus, tensile strength, elongation at break, flexural modulus, flexural strength, and notched Izod strength have been measured. The results show that Young's modulus and strengths have been improved along with the addition of low content of HNTs. Moreover, the gain of notched Izod impact strength obtained by the addition of short kenaf fibers was maintained in hybrids with low concentrations of HNTs. Finally, the thermogravimetric analysis shows that at 10% and 50% weight loss, the thermal degradation rate of the PP and PP/kenaf biocomposites decreased by the addition of HNTs.

The Role of Interfacial Interactions on the Functional Properties of Ethylene-Propylene Copolymer Containing SiO2 Nanoparticles.

In this paper, the mechanical properties, thermal stability, and transparency of ethylene-propylene copolymer (EPC) elastomer modified with various weight percentages (1, 3, and 5 wt.%) of SiO2 nanofillers have been studied. The nanocomposites were prepared via a simple melt mixing method. The morphological results revealed that the nanofillers were uniformly dispersed in the elastomer, where a low concentration of SiO2 (1 wt.%) had been added into the elastomer. The FTIR showed that there are interfacial interactions between EPC matrix and silanol groups of SiO2 nanoparticles. Moreover, by the addition of 1 wt.% of SiO2 in the EPC, the tensile strength and elongation at break of EPC increased by about 38% and 27%, respectively. Finally, all samples were optically transparent, and the transparency of the nanocomposites reduced by increasing the content of SiO2 nanoparticles.

Comparing Multi-Walled Carbon Nanotubes and Halloysite Nanotubes as Reinforcements in EVA Nanocomposites.

The influence of carbon multi-walled nanotubes (MWCNTs) and halloysite nanotubes (HNTs) on the physical, thermal, mechanical, and electrical properties of EVA (ethylene vinyl acetate) copolymer was investigated. EVA-based nanocomposites containing MWCNTs or HNTs, as well as hybrid nanocomposites containing both nanofillers were prepared by melt blending. Scanning electron microcopy (SEM) images revealed the presence of good dispersion of both kinds of nanotubes throughout the EVA matrix. The incorporation of nanotubes into the EVA copolymer matrix did not significantly affect the crystallization behavior of the polymer. The tensile strength of EVA-based nanocomposites increased along with the increasing CNTs (carbon nanotubes) content (increased up to approximately 40% at the loading of 8 wt.%). In turn, HNTs increased to a great extent the strain at break. Mechanical cyclic tensile tests demonstrated that nanocomposites with hybrid reinforcement exhibit interesting strengthening behavior. The synergistic effect of hybrid nanofillers on the modulus at 100% and 200% elongation was visible. Moreover, along with the increase of MWCNTs content in EVA/CNTs nanocomposites, an enhancement in electrical conductivity was observed.

Enhanced Functional Properties of Low-Density Polyethylene Nanocomposites Containing Hybrid Fillers of Multi-Walled Carbon Nanotubes and Nano Carbon Black.

In this work, hybrid filler systems consisting of multi-walled carbon nanotubes (MWCNTs) and nano carbon black (nCB) were incorporated by melt mixing in low-density polyethylene (LDPE). To hybrid systems a mixture of MWCNTs and nCB a mass ratio of 1:1 and 3:1 were used. The purpose was to study if the synergistic effects can be achieved on tensile strength and electrical and thermal conductivity. The dispersion state of carbon nanofillers in the LDPE matrix has been evaluated with scanning electron microscopy. The melting and crystallization behavior of all nanocomposites was not significantly influenced by the nanofillers. It was found that the embedding of both types of carbon nanofillers into the LDPE matrix caused an increase in the value of Young's modulus. The results of electrical and thermal conductivity were compared to LDPE nanocomposites containing only nCB or only MWCNTs presented in earlier work LDPE/MWCNTs. It was no synergistic effects of nCB in multi-walled CNTs and nCB hybrid nanocomposites regarding mechanical properties, electrical and thermal conductivity, and MWCNTs dispersion. Since LDPE/MWCNTs nanocomposites exhibit higher electrical conductivity than LDPE/MWCNTs + nCB or LDPE/nCB nanocomposites at the same nanofiller loading (wt.%), it confirms our earlier study that MWCNTs are a more efficient conductive nanofiller. The presence of MWCNTs and their concentration in hybrid nanocomposites was mainly responsible for the improvement of their thermal conductivity.

Environmentally Friendly Polymer Blends Based on Post-Consumer Glycol-Modified Poly(Ethylene Terephthalate) (PET-G) Foils and Poly(Ethylene 2,5-Furanoate) (PEF): Preparation and Characterization.

Environmentally friendly polymer blends between post-consumer PET-G and bio-based poly(ethylene 2,5 furanoate) (PEF) have been prepared. The PET-G granules were obtained from the post-consumer glycol-modified poly(ethylene terephthalate) PET-G foils from Nicrometal S.A. as a result of materials recycling. PEF was synthesized from dimethyl furan-2,5-dicarboxylate and 1,2-ethylene glycol (BioUltra) by a two-stage melt polycondensation process. According to the calculations followed by Hoy's method, one has studied the miscibility of the components in the blend. The molecular structure of PET-G/PEF blends was analyzed by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy, while the morphology of the blends was determined by Scanning Electron Microscopy (SEM). To evaluate phase transition temperatures, as well as the thermal effects in PET-G/PEF blends, Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA), and Thermogravimetric Analysis (TGA), were performed. Tensile tests revealed that along with an increase in the amount of PEF, an increase in Young's modulus was observed. Besides, the existence of interfacial interactions between polymers, especially in the case of PET-G/PEF 80/20, enabling the PET-G chains to form a network structure with the PEF by reacting with their functional groups, allows observation of a synergistic effect in the improvement of thermal stability and water absorption.

Green Highly Clay-Filled Polyethylene Composites as Coating Materials for Cable Industry-A New Application Route of Non-Organophilised Natural Montmorillonites in Polymeric Materials.

In order to develop flame retardant and relatively green cable coating materials, polyethylene (PE) was melt blended with 5, 7.5, or 10 wt. % of a natural calcium montmorillonite (C-Ca) pre-dispersed in EBA (ethylene-butyl acrylate copolymer), EVA (ethylene-vinyl acetate copolymer), or mEVA (EVA modified with maleic anhydride). For comparison, an organophilised montmorillonite (CW9) was tested. The main study of composites containing EBA/C-Ca, EVA/C-Ca, and mEVA/CW9 pre-dispersions revealed that both clays were not fully exfoliated in the matrix, however, C-Ca (7.5 wt. %) markedly increased limited oxygen index (LOI) from 18% O2 (PE) up to 22.0% O2. An insignificantly higher LOI value (22.2% O2) was noted for a sample with 10 wt. % of CW9. The fillers did not affect hardness, but spectacularly increased Young's modulus of the compression-moulded samples (tensile strength and elongation at break values were reduced). Thermal features of the matrix were not unpredictably changed by the clays. Generally, all the tests revealed that PE filled with the chemically untreated natural C-Ca reached similar or better mechanical and thermal features than materials containing the ammonium salt-modified montmorillonite.

Laser-Induced Periodic Surface Structuring of Poly(trimethylene terephthalate) Films Containing Tungsten Disulfide Nanotubes.

We report the study of the formation of Laser Induced Periodic Surface Structures (LIPSS), with UV femtosecond laser pulses (λ = 265 nm), in free-standing films of both Poly(trimethylene terephthalate) (PTT) and the composite PTT/tungsten disulfide inorganic nanotubes (PTT-WS2). We characterized the range of fluences and number of pulses necessary to induce LIPSS formation and measured the topography of the samples by Atomic Force Microscopy, the change in surface energy and contact angle using the sessile drop technique, and the modification in both Young's modulus and adhesion force values with Peak Force-Quantitative Nanomechanical Mapping. LIPSS appeared parallel to the laser polarization with a period close to its wavelength in a narrow fluence and number of pulses regime, with PTT-WS2 needing slightly larger fluence than raw PTT due to its higher crystallinity and heat diffusion. Little change was found in the total surface energy of the samples, but there was a radical increase in the negative polar component (γ-). Besides, we measured small variations in the samples Young's modulus after LIPSS formation whereas adhesion is reduced by a factor of four. This reduction, as well as the increase in γ-, is a result of the modification of the surface chemistry, in particular a slight oxidation, during irradiation.

Functional Properties of Poly(Trimethylene Terephthalate)-Block-Poly(Caprolactone) Based Nanocomposites Containing Graphene Oxide (GO) and Reduced Graphene Oxide (rGO).

This work reports a study on the influence of graphene oxide (GO) and reduced graphene oxide (rGO) on the functional properties of poly(trimethylene terephthalate)-block-poly(caprolactone) (PTT-block-PCL-T) (75/25 wt.%/wt.%) copolymer, obtained from dimethyl terephthalate (DMT), 1,3-biopropanediol and polycaprolactone diol (PCL) via in situ polymerization. The article presents, if and how the reduction of graphene oxide, in comparison to the non-reduced one, can affect morphological, thermal, electrical and mechanical properties. SEM examination confirms/reveals the homogeneous distribution of GO/rGO nanoplatelets in the PTT-block-PCL-T copolymer matrix. More than threefold increase in the value of the tensile modulus is achieved by the addition of 1.0 wt.% of GO and rGO. Moreover, the thermal conductivity and thermal stability of the GO and rGO-based nanocomposites are also improved. The differential scanning calorimetry (DSC) measurement indicates that the incorporation of GO and rGO has a remarkable impact on the crystallinity of the nanocomposites (an increase of crystallization temperature up to 58 °C for nanocomposite containing 1.0 wt.% of GO is observed). Therefore, the high performances of the PTT-block-PCL-T-based nanocomposites are mainly attributed to the uniform dispersion of nanoplatelets in the polymer matrix and strong interfacial interactions between components.

Electrically and Thermally Conductive Low Density Polyethylene-Based Nanocomposites Reinforced by MWCNT or Hybrid MWCNT/Graphene Nanoplatelets with Improved Thermo-Oxidative Stability.

In this paper, the electrical and thermal conductivity and morphological behavior of low density polyethylene (LDPE)/multi-walled carbon nanotubes (MWCNTs) + graphene nanoplatelets (GNPs) hybrid nanocomposites (HNCs) have been studied. The distribution of MWCNTs and the hybrid of MWCNTs/GNPs within the polymer matrix has been investigated with scanning electron microscopy (SEM). The results showed that the thermal and electrical conductivity of the LDPE-based nanocomposites increased along with the increasing content of carbon nanofillers. However, one could observe greater improvement in the thermal and electrical conductivity when only MWCNTs have been incorporated. Moreover, the improvement in tensile properties and thermal stability has been observed when carbon nanofillers have been mixed with LDPE. At the same time, the increasing content of MWCNTs and MWCNTs/GNPs caused an increase in the melt viscosity with only little effect on phase transition temperatures.

Phase Separation and Elastic Properties of Poly(Trimethylene Terephthalate)-block-poly(Ethylene Oxide) Copolymers.

A series of poly(trimethylene terephthalate)-block-poly(ethylene oxide) (PTT-b-PEOT) copolymers with different compositions of rigid PTT and flexible PEOT segments were synthesized via condensation in the melt. The influence of the block length and the block ratio on the micro-separated phase structure and elastic properties of the synthesized multiblock copolymers was studied. The PEOT segments in these copolymers were kept constant at 1130, 2130 or 3130 g/mol, whereas the PTT content varied from 30 up to 50 wt %. The phase separation was assessed using differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The crystal structure of the synthesised block copolymers and their microstructure on the manometer scale was evaluated by using WAXS and SAXS analysis. Depending on the PTT/PEOT ratio, but also on the rigid and flexible segment length in PTT-b-PEO copolymers, four different domains were observed i.e.,: a crystalline PTT phase, a crystalline PEO phase (which exists for the whole series based on three types of PEOT segments), an amorphous PTT phase (only at 50 wt % content of PTT rigid segments) and an amorphous PEO phase. Moreover, the elastic deformability and reversibility of PTT-b-PEOT block copolymers were studied during a cyclic tensile test. Determined values of permanent set resultant from maximum attained stain (100% and 200%) for copolymers were used to evaluate their elastic properties.