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A racemic mixture of two stereoregular polylactides (PLAs) (i.e. PLLA and PDLA) allows obtaining wholly amorphous stereocomplex PLA films by solvent casting method. The amorphous phase behavior of stereocomplex PLA is compared with that of PLLA and PDLA by advanced thermal analysis, such as Fast Scanning Calorimetry (FSC) and Dielectric Relaxation Spectroscopy (DRS). FSC allows us to quench at very high cooling rate (up to 4000 K・s–1) the studied polymers and to obtain glassy amorphous phases with high excess of enthalpy. It is shown that stereocomplexation has no influence on the glass transition temperature, the physical aging and on the cooperativity. The α and β processes were examined to study the dielectric properties, such as relaxation time, dielectric strength, and fragility. The results of FSC and DRS are correlated to determine the values of cooperativity length which are found to be similar in a wide temperature range. It is found that the studied polymers have the similar dielectric properties independently on their tacticity.

Novel tough bio-based polyesters poly(ethylene 2,5-thiophenedicarboxylate-co-1,4-cyclohexanedimethylene 2,5-thiophenedicarboxylate)s (PECTFs) were synthesized from 2,5-thiophenedicarboxylic acid (TDCA), 1,4-cyclohexanedimethanol (CHDM) and ethylene glycol (EG). The microstructure, thermal and mechanical properties were investigated. Poly(ethylene 2,5-thiophenedicarboxylate) (PETF) displayed the glass transition temperature (~64 °C) and tensile strength (~72 MPa) similar to poly(ethylene terephthalate) (PET). However, the nonlinear structure of TDCA resulted in an angle of 148° between carboxylic acid carbons and the S atom resulted in a permanent dipole, so the thiophene ring-flipping was hindered and the low elongation at break (~24%) was observed for PETF. The peak corresponding to the secondary relaxation shifted to lower temperature due to the incorporation of CHDM, which yielded ductile copolyesters with high elongation at break. When the CHDM content was equal to or higher than 29%, a high elongation at break (>160%) was observed.

A stable and reproducible bi-component melt spinning process on an industrial scale incorporating Phase Change Material (PCM) into textile fibres has been successfully developed and carried out using a melt spinning machine. The key factor for a successful bi-component melt spinning process is that a deep insight into the thermal and rheological behaviour of PCM using Difference Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), and an oscillatory rheological investigation. PCM is very sensitive to the temperature and residence time of the melt spinning process. It is found that the optimal process temperature of PCM is 210 °C. The textile-physical properties and the morphology of the melt spun and further drawn bi-component core and sheath fibres (bico fibres) were investigated and interpreted. The heat capacities of PCM incorporated in bico fibres were also determined by means of DSC. The melt spun bico fibres integrating PCM provide a high latent heat of up to 22 J/g, which is three times higher than that of state-of-the-art fibres, which were also obtained using the melt spinning process. Therefore, they have the potential to be used as smart polymer fibres for textile and other technical applications.

In the current manuscript, a new approach for the synthesis of poly(1,4- cyclohexanedimethylene 2,6-naphthalate) (PCHDMN) derived from dimethyl 2,6-naphthalenedicarboxylate (2,6-DMN) and 1,4-Cyclohexanedimethanol (CHDM) via melt polycondensation method is introduced. The effect of three different synthesis pathways, polycondensation time and temperature on polyesters molecular weight increase has been investigated. All of the prepared samples were characterized measuring their intrinsic viscosity (IV), thermal properties and morphology with differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD), respectively. The results demonstrated the effectiveness of the synthesis pathway proposed for the preparation of PCHDMN, resulting in high molecular weight (IV value around 0.5 dL/g) and much shorter reaction time. Melt polycondensation temperatures above melting point of polyester should be avoided to be used due to the decomposition of polyester. This was proved by thermogravimetric analysis (TGA) and Pyrolysis-gas chromatography–mass spectroscopy analysis (Py-GC/MS).

Poly(trimethylene 2,5-furanoate) (PTF) nanocomposites reinforced with few layer graphene (FLG) were prepared through in situ polymerization. The method in question allows obtaining well-dispersed nanoplatelets in the whole volume of PTF matrix. The mechanical properties of the PTF/FLG nanocomposites slightly increased with as quantity of FLG as small as 0.1 wt%, which was best seen in the improvement of elongation at break by about two times. The presence of FLG did not affect the crystallization and chain mobility of PTF matrix. However, the incorporation of a small quantity of FLG slightly improved the thermal stability of the nanocomposites. Additionally, the cold and hot water absorption and oxygen permittivity measurements confirmed that FLG affected the tortuosity of the diffusive path for the penetrant molecule. Moreover, along with a successive addition of FLG a linear increase in thermal conductivity was visible.

Binary blends composed of 1,3-bis (3,4-dicyanophenoxy) benzene (3BOCN) and ionic liquids (ILs) with different molecular structures were prepared. The curing behavior of these 3BOCN/ILs blends were studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and rheological analysis. The study suggested that the blends possessed a wide processing window and the structures of ILs (anion, cation and alkyl chain length at cation) had an effect on curing behavior. The 3BOCN/[EPy]BF4 resins were prepared at elevated temperature. IR spectra of the resins showed that there were triazine and isoindoline formed in curing process. The TGA and dynamic mechanical analysis (DMA) revealed that the resins have excellent thermal stability together with high storage modulus and high glass transition temperature (Tg). Dielectric properties, long term oxidative aging and water uptake measurements of the resins suggested the IL brought some unique properties to the resins.

A new bio-based elastomer, poly(butylene 2,5-furandicarboxylate-ε-caprolactone) (PBFCL), has been synthesized from 2,5-furandicarboxylic acid, 1,4-butanediol, and ε-caprolactone successfully for the first time. The obtained copolyester was characterized in terms of chemical structure, thermal and mechanical properties, and enzymatic degradability. In PBFCL elastomer, butylene-2,5-furandiacrboxylate units (hard segments) crystallize to serve as physical crosslinks while ε-caprolactone polyester diol (soft segments) provide flexibility. PBFCL is a multi-blocked copolyester with randomly distributed rigid and soft segments. It possesses original feature of high strength and biodegradability stemming from the uses of aromatic and aliphatic monomers respectively. An important aspect of this new furanic-aliphatic polyester is its tailor-made properties simply achieved by changing the content of hard or soft segments. Typically, PBFCL-40 of optimal composition has Young’s modulus as low as 15.4 MPa, tensile strength as high 24.8 MPa, and elongation as long as 885%.

A polyimide (PI) aerogel with excellent combined thermal and dielectric properties was successfully prepared by the polycondensation of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 5-amino-2-(4-aminophenyl)benzoxazole (APBO) and octa(amino-phenyl)silsesquioxane (OAPS) crosslinker, followed by a supercritical carbon dioxide (scCO2) drying treatment. The developed PI aerogel exhibited an ultra-low dielectric constant (k) of 1.15 at a frequency of 2.75 GHz, a volume resistivity of 5.45·10 14 Ω·cm, and a dielectric strength of 132 kV/cm. The flexible PI aerogel exhibited an open- pore microstructure consisting of three-dimensional network with tangled nanofibers morphology with a porosity of 85.6% (volume ratio), an average pore diameter of 19.2 nm, and a Brunauer-Emmet-Teller (BET) surface area of 428.6 m 2 /g. In addition, the PI aerogel showed excellent thermal stability with a glass transition temperature (Tg) of 358.3 °C, a 5% weight loss temperature over 500 °C, and a residual weight ratio of 66.7% at 750 °C in nitrogen.

© BME-PT. In the present study, the effect of nano magnetite (Fe3O4) content on structural, dielectric/electrical, magnetic and thermal properties of poly(vinylidene fluoride)/carbon nanotubes matrix, is investigated. Nanocomposite films of polyvinylidene fluoride, carbon nanotubes and Fe3O4nanoparticles were prepared by the twin screw compounding method. Fe3O4, as magnetic inclusions was incorporated into the composites with carbon nanotubes loadings well above the percolation threshold, where conductive networks were formed. Magnetic characterization revealed the ferrimagnetic behavior of nanocomposites, with saturation magnetization values depending on magnetite content. Results obtained from the analysis of Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC) techniques were very informative for the study of the polymorphism and crystallinity in PVDF. The incorporation of Fe3O4inclusions in PVDF/CNT matrix, gradually increase both electrical conductivity and dielectric permittivity up to 10 wt% Fe3O4content, while at the higher Fe3O4 content (15 wt%) reduced values were obtained. This behavior, at higher Fe3O4content, should be possible related to the insulating and barrier role of Fe3O4nanoparticles.

UV photo-oxidation was first applied to fabricate superhydrophobic polyimide (PI) films in combination with fluoroalkylsilane (FAS) modification. During prolonged UV irradiation, commercial flat PI films evolved to form unique micro/nanostructures. Meanwhile, the root mean square (RMS) surface roughness increased from 1.74 to 53.70 nm, leading to a gradual increase of WCA from 105.1 to 159.2° after FAS treatment. After 72 h of UV radiation exposure, the micro/nano-structured and FAS-modified PI films exhibited superhydrophobicity with water contact angle (WCA) larger than 150° and sliding angle (SA) less than 5°. The superhydrophobicity remained even after annealing at 350°C, which enabled stable utilization under elevated temperature. Stable micro/nanostructures and chemical bonding of FAS were found to contribute to the high thermal endurance. Moreover, the formation mechanism of the superhydrophobic PI films was investigated. The proposed UV photo-oxidation method provides a new route for the industrial fabrication of thermally stable superhydrophobic PI films.

nonylphenoxy-1, 2-dinitrilbenzene (NP-ph), a novel kind of phthalonitrile containing flexible hydrocarbyl chains, has been synthesized. The structures of NP-ph were investigated by Nuclear Magnetic Resonance Spectroscopy ( 1 H-NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Low viscosity NP-ph/phthalonitrile containing benzox- azine (BA-ph) blends were achieved by melt blending BA-ph with various content of NP-ph. Copolymerization behaviors and processability of NP-ph/BA-ph have been investigated by Differential Scanning Calorimetry (DSC) and Dynamic Rhe- ological Analysis. Results indicated that NP-ph/BA-ph blends processability was improved and can be controlled by vary- ing NP-ph contents, processing temperature and time. NP-ph/BA-ph polymers were prepared from the thermal polymerization with short curing time and low curing temperatures without addition of any other curing agents, which dis- played high glass transition temperature (>360°C) and attractive thermal decomposition temperature (>420°C). The out- standing glass transition temperature and desirable thermo-oxidative stabilities, together with good processability and sound process conditions could enable the NP-ph/BA-ph polymers to be further explored in the fields under some practical critical circumstances with requirements of high wears and temperatures.

Present work reports novel synthesis of Polyaniline (PANI)/Se nanocomposites. Se nanowires are prepared from SeO2 under assistance of vitamin C and polyaniline is synthesized through chemical oxidation. The effect of composition of Se nanowires on the properties of polyaniline was investigated and five orders increase in conductivity after doping has been observed. The electrical properties of nanocomposites show that conduction is through hopping process due to the wide range of localized states present near fermi level. FTIR (Fourier Transform Infrared spectroscopy) and ultraviolet (UV)-visible studies confirm the occurrence of polyaniline in conducting emeraldine salt form in the composites and sug- gest incorporation of Se in polymer. The optical studies indicate that absorption mechanism is due to indirect allowed tran- sition and the optical band gap tends to decrease after doping. The thermal stability of composites has been ascertained on the basis of DSC (Differential Scanning Calorimetery) measurements. TEM (Transmission Electron Microscopy) and SEM (Scanning Electron Microscopy) analysis have also been carried out for morphological studies.

The object of this study was to investigate how different decreasing of pH regimes during microencapsulation process with melamine-formaldehyde (MF) resin affects the composition, morphology and thermal stability of microcap- sules containing a phase-change material (PCM). Technical butyl stearate was used as PCM. Microencapsulation was car- ried out at 70°C. For all experiments the starting pH value was 6.0. After one hour of microencapsulation at the starting pH value, the pH value was lowered to final pH value (5.5; 5.0; 4.5) in a stepwise or linear way. The properties of microcap- sules were monitored during and after the microencapsulation process. The results showed that pH value decreasing regime was critical for the morphology and stability of microcapsules. During microencapsulations with a stepwise decrease of pH value we observed faster increase of the amount of MF resin in the microencapsulation product compared to the microen- capsulations with a linear pH value decrease. However, faster deposition in the case of microencapsulations with stepwise decrease of pH value did not result in thicker MF shells. The shell thickness increased much faster when the pH value was decreased in a linear way or in several smaller steps. It was shown that for the best thermal stability of microcapsules, the pH value during microencapsulation had to be lowered in a linear way or in smaller steps to 5.0 or lower.

In order to enhance the adhesion between inorganic particles and polymer matrix, in this paper, the mesoporous silica SBA-15 material was synthesized by the sol-gel method. The surface of SBA-15 was modified using γ-glycidyloxypropyltrimethoxysilane (GOTMS) as a coupling agent, and then mesoporous silica/phenolic resin (SBA-15/PF) nanocomposites were prepared via in situ polymerization. The structural parameters and physical properties of SBA-15, SBA-15-GOTMS (SBA-15 surface treated using GOTMS as coupling agents) and E-SBA-15/PF (SBA-15/PF nanocomposites extracted using ethanol as solvent) were characterized by X-ray diffraction (XRD), N2 adsorption-desorption, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The thermal properties of the nanocomposites were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results demonstrated that the GOTMS were successfully grafted onto the surface of SBA-15, and chemical bonds between PF and SBA-15-GOTMS were formed after in situ polymerization. In addition, it is found that the in situ polymerization method has great effects on the textural parameters of SBA-15. The results also showed that the glass transition temperatures and thermal stability of the PF nanocomposites were obviously enhanced as compared with the pure PF at silica contents between 1–3 wt%, due to the uniform dispersion of the modified SBA-15 in the matrix.

We report the preparation, mechanisms and thermal properties of core-shell structured polymer/inorganic nanoparticle composite microspheres prepared by Pickering emulsion polymerization. Stable Pickering emulsion was firstly fabricated by using surface-modified nano-SiO2 particles as stabilizer. And then, two kinds of polystyrene/nano-SiO2 (PS/SiO2) composite microspheres with different sizes and morphologies were synthesized using hydrophobic azobisisobu- tyronitrile (AIBN) and hydrophilic ammonium persulfate (APS) as initiator, respectively. The possible mechanisms of Pickering emulsion polymerization initiated by different initiators were proposed according to the results of transmission electron microscope (TEM) and scanning electron microscope (SEM). The chemical structure and molecular weight of the composite microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometer (XRD) and gel permeation chromatography coupled with a multi-angle laser light scattering photometer (GPC-MALLS). Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were used to comparatively analyze the thermal properties of nanocomposites and corresponding pure polymer. The results indicated that the decomposition tem- perature and glass transition temperature (Tg) of nanocomposites were elevated to a certain degree due to the existence of nano-SiO2.

The encapsulation of octadecane (OD) as heat storage material was studied. The core-shell polydivinylbenzene (PDVB)/natural rubber (NR) capsules encapsulating OD was prepared using the Self-assembling of Phase Separated Poly- mer (SaPSeP) method by suspension polymerization. The mixture of dispersed phase consisting of DVB, NR, OD and ben- zoyl peroxide was added in polyvinyl alcohol aqueous solution and then homogenized at 5,000 rpm for 5 minutes. The obtained monomer droplet emulsion was subsequently polymerized at 80°C for 8 hours resulting in PDVB/NR capsule encapsulating OD. The influence of molecular weight and content of NR on the encapsulation efficiency and thermal prop- erties of the encapsulated OD were investigated. It was found that both factors affected on the preparation of PDVB/ NR/OD capsule. High molecular weight NR restricted phase separation of formed PDVB. High NR content also reduced phase separation of PDVB due to the increase of internal viscosity. Then, only the incorporation of appropriate molecular weight and content of NR resulted in the formation of PDVB/NR/OD capsule.