Polymers, Volume 9, Issue 10 (October 2017) – 86 articles

Crystallization of all-aromatic heterocyclic polymers typically results in an improvement of their thermo-mechanical properties. Nucleation agents may be used to promote crystallization, and it is well known that the incorporation of nanoparticles, and in particular carbon-based nanofillers, may induce or accelerate crystallization through nucleation. The present study addresses the structural properties of polyetherimide-based nanocomposites and the initial stages of polyetherimide crystallization as a result of single-walled carbon nanotube (SWCNT) incorporation. We selected two amorphous thermoplastic polyetherimides ODPA-P3 and aBPDA-P3 based on 3,3′,4,4′-oxydiphthalic dianhydride (ODPA), 2,3′,3,4′-biphenyltetracarboxylic dianhydride (aBPDA) and diamine 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene (P3) and simulated the onset of crystallization in the presence of SWCNTs using atomistic molecular dynamics. For ODPA-P3, we found that the planar phthalimide and phenylene moieties show pronounced ordering near the CNT (carbon nanotube) surface, which can be regarded as the initial stage of crystallization. We will discuss two possible mechanisms for ODPA-P3 crystallization in the presence of SWCNTs: the spatial confinement caused by the CNTs and π–π interactions at the CNT-polymer matrix interface. Based on our simulation results, we propose that ODPA-P3 crystallization is most likely initiated by favorable π–π interactions between the carbon nanofiller surface and the planar ODPA-P3 phthalimide and phenylene moieties. Full article

This detailed study reveals the relation between structural evolution and the mechanical response of $\alpha$ -, $\beta$ - and $\gamma$ -iPP. Uni-axial compression experiments, combined with in situ WAXD measurements, allowed for the identification of the evolution phenomena in terms of phase composition. Tensile experiments in combination with SAXS revealed orientation and voiding phenomena, as well as structural evolution in the thickness of the lamellae and amorphous layers. On the level of the crystallographic unit cell, the WAXD experiments provided insight into the early stages of deformation. Moreover, transitions in the crystal phases taking place in the larger deformation range and the orientation of crystal planes were monitored. At all stretching temperatures, the crystallinity decreases upon deformation, and depending on the temperature, different new structures are formed. Stretching at low temperatures leads to crystal destruction and the formation of the oriented mesophase, independent of the initial polymorph. At high temperatures, above $T{\alpha }_c$ , all polymorphs transform into oriented $\alpha$ -iPP. Small quantities of the initial structures remain present in the material. The compression experiments, where localization phenomena are excluded, show that these transformations take place at similar strains for all polymorphs. For the post yield response, the strain hardening modulus is decisive for the mechanical behavior, as well as for the orientation of lamellae and the evolution of void fraction and dimensions. $\beta$ -iPP shows by far the most intense voiding in the entire experimental temperature range. The macroscopic localization behavior and strain at which the transition from disk-like void shapes, oriented with the normal in tensile direction, into fibrillar structures takes place is directly correlated with the strain hardening modulus. Full article

Based on hydrogen bonding, the highly uniform polyaniline (PANI) nanotubes were synthesized by self-assembly method using citric acid (CA) as the dopant and the structure-directing agent by optimizing the molar ratio of CA to aniline monomer (Ani). Synthesis conditions like reaction temperature and mechanical stirring were considered to explore the effects of hydrogen bonding on the morphologies. The effects of CA on the final morphology of the products were also investigated. The as-synthesized CA doped polyaniline (PANI) nanomaterials were further deposited on the plate electrodes for the test of gas sensing performance to ammonia (NH₃). The sensitivity to various concentrations of NH₃, the repeatability, and the stability of the sensors were also tested and analyzed. As a result, it was found that the PANI nanomaterial synthesized at the CA/Ani molar ratio of 0.5 has highly uniform tubular morphology and shows the best sensing performance to NH₃. It makes the PANI nanotubes a promising material for high performance gas sensing to NH₃. Full article

Magnetic molecularly imprinted polymers (MMIPs), combination of outstanding magnetism with specific selective binding capability for target molecules, have proven to be attractive in separation science and bio-applications. Herein, we proposed the core–shell magnetic molecularly imprinted polymers for food analysis, employing the Fe₃O₄ particles prepared by co-precipitation protocol as the magnetic core and MMIP film onto the silica layer as the recognition and adsorption of target analytes. The obtained MMIPs materials have been fully characterized by scanning electron microscope (SEM), Fourier transform infrared spectrometer (FT-IR), vibrating sample magnetometer (VSM), and re-binding experiments. Under the optimal conditions, the fabricated Fe₃O₄@MIPs demonstrated fast adsorption equilibrium, a highly improved imprinting capacity, and excellent specificity to target sterigmatocystin (ST), which have been successfully applied as highly efficient solid-phase extraction materials followed by high-performance liquid chromatography (HPLC) analysis. The MMIP-based solid phase extraction (SPE) method gave linear response in the range of 0.05–5.0 mg·L⁻¹ with a detection limit of 9.1 µg·L⁻¹. Finally, the proposed method was used for the selective isolation and enrichment of ST in food samples with recoveries in the range 80.6–88.7% and the relative standard deviation (RSD) <5.6%. Full article

The surface and protein adsorption properties of 316L stainless steel (316L SS) modified with polycaprolactone (PCL) films are systematically investigated. The wettability of the PCL films was comparable to that of bare 316L SS because the rough surface morphology of the PCL films counteracts their hydrophobicity. Surface modification with PCL film significantly improves the corrosion resistance of the 316L SS because PCL is insulating in nature. A coating of PCL film effectively reduces the amount of adhered bovine serum albumin (BSA) on the surface of 316L SS in a bicinchoninic acid protein assay. PCL is both biodegradable and biocompatible, suggesting the potential for the surface modification of implants used in human bodies; in these applications, excellent corrosion resistance and anticoagulant properties are necessary. Full article

A carbazole-based polymer (poly(tris(4-carbazoyl-9-ylphenyl)amine) (PtCz)) is electrosynthesized on an indium tin oxide (ITO) electrode. PtCz film displays light yellow at 0.0 V, earthy yellow at 1.3 V, grey at 1.5 V, and dark grey at 1.8 V in 0.2 M LiClO₄/ACN/DCM (ACN/DCM = 1:3, by volume) solution. The ΔT and coloration efficiency (η) of PtCz film are 30.5% and 54.8 cm²∙C⁻¹, respectively, in a solution state. Three dual-type electrochromic devices (ECDs) are fabricated using the PtCz as the anodic layer, poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,3-dimethyl-3,4-dihydro-thieno[3,4-b][1,4]dioxepine) (PProDOT-Me₂), and poly(3,4-(2,2-diethylpropylenedioxy)thiophene) (PProDOT-Et₂) as the cathodic layers. PtCz/PProDOT-Me₂ ECD shows high ΔT_max (36%), high η_max (343.4 cm²·C⁻¹), and fast switching speed (0.2 s) at 572 nm. In addition, PtCz/PEDOT, PtCz/PProDOT-Me₂, and PtCz/PProDOT-Et₂ ECDs show satisfactory open circuit memory and long-term stability. Full article

In this study, a new diamine monomer, namely 4,4′-diamino-4″-(5H-dibenzo[b,f]azepin-5-yl)triphenylamine, was prepared and polymerized with four kinds of dicarboxylic acids via direct polycondensation reaction resulting in a novel series of soluble and electroactive polyamides (PAs). The tough thin films of all PAs could be solution-cast onto an indium-tin oxide (ITO)-coated glass substrate owing to the good solubility in polar organic solvents. Two pairs of obvious redox peaks for these films were observed in cyclic voltammetry (CV) with low onset potentials (E_onset) of 0.37–0.42 V accompanying with remarkable reversible color changes between light yellow and dark blue. A new absorption peak at around 915 nm emerged in near infrared (NIR) spectra; the increasing potential indicated that PAs could be used as a NIR electrochromic material. Moreover, the PAs showed high coloration efficiency (CE; η) in the range of 190–259 cm² C⁻¹. Full article

The present work aimed at developing fully green composites from renewable materials, i.e., acrylated epoxidized soybean oil (AESO) and microcrystalline cellulose (MCC) by a solution casting method. The reinforcing effect of MCC on AESO resins was optimized by adjusting MCC loading from 20 to 40 wt % in terms of physical, mechanical, and thermal properties as well as water absorption of the resulting MCC/AESO composites. The interaction between MCC and AESO was characterized by Fourier transform infrared (FTIR) analysis, which revealed possible hydrogen bonds between the –OH groups of MCC along with the polar components of AESO including C=O, –OH, and epoxy groups. This was further evidenced by a benign interfacial adhesion between MCC and AESO resins as revealed by scanning electron microscope (SEM) analysis. The incorporation of MCC into AESO resins significantly increased the density, hardness, flexural strength, and flexural modulus of the MCC/AESO composites, indicative of a significant reinforcing effect of MCC on AESO resins. The composite with 30 wt % MCC obtained the highest physical and mechanical properties due to the good dispersion and interfacial interaction between MCC and AESO matrix; the density, hardness, flexural strength, and flexural modulus of the composite were 15.7%, 25.0%, 57.2%, and 129.7% higher than those of pure AESO resin, respectively. However, the water resistance at room temperature and 100 °C of the composites were dramatically decreased due to the inherent hydrophilicity of MCC. Full article

Amphiphilic copolymers were obtained by grafting azide-terminated polyglycidol, poly(ethylene oxide), or poly(2-hydroxyethyl acrylate) chain segments onto alkyne-functionalized arborescent poly(γ-benzyl l-glutamate) (PBG) cores of generations G1–G3 via copper(I)-catalyzed azide–alkyne Huisgen cycloaddition (CuAAC) coupling. The alkyne functional groups on the arborescent PBG substrates were either distributed randomly or located exclusively at the end of the chains added in the last grafting cycle of the core synthesis. The location of these coupling sites influenced the ability of the arborescent copolymers to form unimolecular micelles in aqueous environments: The chain end grafting approach provided enhanced dispersibility in aqueous media and favored the formation of unimolecular micelles in comparison to random grafting. This is attributed to a better defined core-shell morphology for the copolymers with end-grafted shell segments. Aqueous solubility also depended on the type of material used for the shell chains. Coupling by CuAAC opens up possibilities for grafting a broad range of polymers on the arborescent substrates under mild conditions. Full article

Nature as the ultimate inspiration can direct, gate, and selectively transport species across channels to fulfil a specific targeted function. Harnessing such precision over local structure and functionality at the nanoscale is expected to lead to indispensable developments in synthetic channels for application in catalysis, filtration and sensing, and in drug delivery. By combining mesoporous materials with localised charge-switchable poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes, precisely controlling pore filling and exploring the possibility of incorporating two different responsive polymers, we hope to approach the precision control of natural systems in the absence of an external force. Here, we report a simple one-step approach to prepare a mesoporous silica thin film with ~8 nm pores functionalised with a photoiniferter by combining sol–gel chemistry and evaporation-induced self-assembly (EISA). We show that surface-initiated photoiniferter-mediated polymerisation (SI-PIMP) allows the incorporation of a high polymer content up to geometrical pore blocking by the simple application of UV light in the presence of a monomer and solvent, proceeding in a controlled manner in pore sizes below 10 nm, with the potential to tune the material properties through the formation of surface-grafted block copolymers. Full article

Seven composite models of meta-aramid fibers with different moisture contents were studied using molecular dynamics simulation. The effects of moisture on the thermal stability and mechanical properties of the fibers and their mechanisms were analyzed, considering characteristics such as hydrogen bonding, free volume, mean square displacement, and mechanical parameters. The simulation results showed that the large number of hydrogen bonds between water molecules and meta-aramid fibers destroyed the original hydrogen-bond network. Hydrogen bonds between the molecular chains of meta-aramid fibers were first destroyed, and their number decreased with increasing moisture content. The free volume of the fibers thereby increased, the interactions between fiber chains weakened with increasing moisture content, and the fiber chain movement intensified accordingly. The ratio of diffusion coefficients of the water molecules to moisture contents of the composite models increased linearly, and the water molecule diffusion increased, which accelerated the rate of damage to the original hydrogen-bond network of the meta-aramid fibers and further reduced their thermal stability. In general, the mechanical properties of the composites were negatively related to their moisture content. Full article

The anionic polymerization of styrene and 1,3-butadiene in the presence of phosphazene bases (t-BuP4, t-BuP2 and t-BuP1), in benzene at room temperature, was studied. When t-BuP1 was used, the polymerization proceeded in a controlled manner, whereas the obtained homopolymers exhibited the desired molecular weights and narrow polydispersity (Ð < 1.05). In the case of t-BuP2, homopolymers with higher than the theoretical molecular weights and relatively low polydispersity were obtained. On the other hand, in the presence of t-BuP4, the polymerization of styrene was uncontrolled due to the high reactivity of the formed carbanion. The kinetic studies from the polymerization of both monomers showed that the reaction rate follows the order of [t-BuP4]/[sec-BuLi] >>> [t-BuP2]/[sec-BuLi] >> [t-BuP1]/[sec-BuLi] > sec-BuLi. Furthermore, the addition of t-BuP2 and t-BuP1 prior the polymerization of 1,3-butadiene allowed the synthesis of polybutadiene with a high 1,2-microstructure (~45 wt %), due to the delocalization of the negative charge. Finally, the one pot synthesis of well-defined polyester-based copolymers [PS-b-PCL and PS-b-PLLA, PS: Polystyrene, PCL: Poly(ε-caprolactone) and PLLA: Poly(L-lactide)], with predictable molecular weights and a narrow molecular weight distribution (Ð < 1.2), was achieved by sequential copolymerization in the presence of t-BuP2 and t-BuP1. Full article

RN1, a polysaccharide from flowers of Panax pseudo-ginsieng Wall. Var. notoginseng (Burkill) Hoo & Tseng, is a potential multi-targeting drug candidate for pancreatic cancer treatment. However, the active targeting domain of RN1 is still unknown. Herein, three RN1 derived branches were synthesized via [3+2] or [2+2] strategies, efficiently. Two pentasaccharides, 18 and 27, showed similar inhibition effect on pancreatic cancer BxPC-3 cells to that of RN1 at same concentration. Interestingly, tetrasaccharide 21 potently inhibited gemcitabineresistant cell line Panc-1 at high concentration. These suggest that the branches of RN1 might be the active targeting domain and tetrasaccharide 21 might be a potential leading compound for pancreatic cancer with gemcitabine resistance. Full article

The formation of micro-cracks and crack propagation is still an acute problem in polymer and polymer composites. These micro-cracks usually occur while the materials are manufactured or serviced. The development and coalescence of these cracks reduces the lifespan and brings about a catastrophic failure of the materials. Novel scientific research on polymeric self-healing is emphasised in a number of publications, which consist of contributions from many of the prominent researchers in this area. Progress in this field can eventually enable scientist to construct new flexible materials that both monitor the material’s integrity and repair the deformed material prior to the occurrence of any fatal failures. This report describes recent trends that have been used in material science and computational methods to mitigate the development of micro-cracks and crack propagation in polymer composites. Full article

Hydrosilylation reactions, the (commonly) anti-Markovnikov additions of silanes to unsaturated bonds present in compounds such as alkenes and alkynes, offer numerous unique and advantageous properties for the preparation of polymeric materials, such as high yields and stereoselectivity. These reactions require to be catalyzed, for which platinum compounds were used in the initial stages. Celebrating the 50th anniversary of hydrosilylations in polymer science and, concomitantly, five decades of continuously growing research, hydrosilylation reactions have advanced to a level that renders them predestined for transfer into commercial products on the large scale. Facing this potential transfer, this review addresses and discusses selected current trends of the scientific research in the area, namely low-cost transition metal catalysts (focusing on iron, cobalt, and nickel complexes), metal-free catalysts, non-thermally triggered hydrosilylation reactions (highlighting stimuli such as (UV-)light), and (potential) industrial applications (highlighting the catalysts used and products manufactured). This review focuses on the hydrosilylation reactions involving alkene reactants. Full article

Silicone rubber (SiR) is used as an insulating material for cables installed in a nuclear power plant. Gamma rays irradiated SiR sheets for various periods at temperatures of 145 and 185 °C, and the resultant changes were analyzed by examining complex permittivity spectra and surface potential decay characteristics. Three different processes, namely, instantaneous polarization, electrode polarization due to the accumulation of ions to form double charge layers at dielectric/electrode interfaces, and DC conduction caused by directional hopping of ions, contribute to the complex permittivity. By fitting the spectra to theoretical equations, we can obtain the dielectric constant at high frequencies, concentration and diffusion coefficient of ions and DC conductivity for the pristine and degraded samples. The instantaneous polarization becomes active with an increase of dose and ageing temperature. The thermal expansion coefficient estimated from the temperature dependence of dielectric constant at high frequencies becomes smaller with an increase in dose, which is in good agreement with the experimental results of the swelling ratio. Additionally, trap distributions are calculated from surface potential decay measurements and analyzed to explain the variation in conductivity. Trap energy increases firstly, and then decreases with an increase in dose, leading to a similar change in DC conductivity. It is concluded that generations of both oxidative products and mobile ions, as well as the occurrence of chain scission and crosslinking are simultaneously induced by gamma rays. Full article

The orientation of reinforcement fillers in composites plays a vital role in their mechanical properties. This paper employs the Mori–Tanaka micromechanics model, incorporating the effect of stretching-induced reorientation of graphene platelets (GPL), to predict Young’s modulus of GPL/polymer nanocomposites. Subjected to uni-axial stretching, dispersion of GPLs is described by an orientation distribution function (ODF) in terms of a stretching strain and two Euler angles. The ODF shows that GPLs tend to realign along the stretching direction. Such realignment is enhanced at a higher Poisson’s ratio and under a larger stretching strain. It is found that the out-of-plane Young’s modulus of GPL nanofillers has a limited effect on the overall Young’s modulus of the composites. With an increase in stretching strain and GPL concentration, Young’s modulus increases in the stretching direction while it decreases in the transverse direction. A larger aspect-ratio of GPLs with fewer layers is preferred for enhancing Young’s modulus in the stretching direction, but it is unfavorable in the transverse direction. Moreover, Young’s moduli in both longitudinal and transverse directions are more sensitive to the reorientation of smaller-sized GPLs with a greater concentration in the composites. Full article

A series of novel chiral nonmetallocene pincer-type rare-earth metal dialkyl complexes bearing the chiral monoanionic tridentate C₂-symmetric 1,3-bis(oxazolinymethylidene)isoindoline (BOXMI-H) ligand (BOXMI)Ln(CH₂SiMe₃)₂ 1–3 (1: Ln = Sc, yield = 57%; 2: Ln = Lu, yield = 55%; 3: Ln = Y, yield = 62%) have been prepared in moderate yields via the acid-base reaction between the BOXMI ligand and rare-earth metal tri(trimethylsilylmethyl) complexes. The X-ray diffractions show that both of the complexes 1 and 2 contain one BOXMI ligand and two trimethylsilylmethyl ligands, adopting a distorted trigonal bipyramidal configuration. In the presence of a cocatalyst such as borate and AlR₃, these complexes 1–3 exhibit high activities of up to 6.8 × 10⁴ (g of polymer)/(mol_Ln h) and high cis-1,4 selectivities of up to 97% in the polymerization of isoprene in toluene, yielding the cis-1,4-polyisoprenes with heavy molecular weights (M_n of up to 710,000 g/mol) and bimodal molecular weight distributions (M_w/M_n = 2.0–4.5). Full article

In this study, polyimide (PI)/Ag nanowire (AgNW) nanocomposite aerogels with extremely high mechanical performance have been fabricated utilizing amine-modified AgNWs as mechanical nanoreinforcement particulates and crosslinking agents. Initially, AgNWs were fabricated and surface modified by p-aminothiophenol (PATP), then the aminated AgNWs were dispersed into polyamide acid solution and aerogels were prepared by supercritical CO₂ drying. Raman and X-ray photoelectron spectroscopy (XPS) spectrometry were carried out on A-AgNWs (aminated Ag nanowires) to prove the successful modification. This functional nanoparticle greatly enhanced the strength and toughness of aerogels without evident increase in densities. Comparing to pure PI aerogels, samples with 2.0 wt % of A-AgNWs had a 148% increase in compression strength and 223% increase in Young’s modulus, which equates to 2.41 and 27.66 MPa, respectively. Simultaneously, the tensile test indicated that aerogels with 2.0 wt % of A-AgNWs had a breaking energy of 40.18 J/m³, which is 112% higher than pure PI aerogels. The results presented herein demonstrate that aminated AgNWs are an innovative cross-linker for PI aerogels and can improve their strength and toughness. These aerogels have excellent potential as high-duty, lightweight porous materials in many areas of application. Full article

Mycotoxins are secondary toxic metabolites that are produced by fungi representing threats to human and animal health. The objective of this study was to evaluate the adsorption capacity of Chitosan (CHI), and three cellulosic polymers (HPMC, CMC, and MCC), on six mycotoxins (AFB₁; FUB₁; OTA; T-2; DON; and, ZEA) using an in vitro digestive model for poultry. The adsorbent capacity of the materials in the supernatant of each compartment was evaluated by a non-competitive chemiluminescent assay. Control groups with no adsorbent material had an adsorption value of 0.00% against all six mycotoxins that were evaluated. All four materials tested showed significant (p < 0.05) binding activity against all of the mycotoxins when compared with the control non-treated group. However HPMC, CMC, and MCC showed better adsorbent capacity when compared with CHI. Full article

In this paper, a dynamic impregnating device, which can generate supersonic vibration with the vacuum-adsorbing field, was used to prepare the hybrid graphene oxide (GO)/polyethylene glycol (PEG). Interestingly, the hybrid GO/PEG under dynamic impregnating and/or internal mixing was introduced into poly-(lactic acid) (PLA) matrix via melting-compounding, respectively. On one hand, compared with the internal mixing, the hybrid GO/PEG with the different component ratio using dynamic impregnation had a better dispersed morphology in the PLA matrix. On the other hand, compared with the high molecular weight (M_w) of PEG, the hybrid GO/PEG with low M_w of PEG had better an exfoliated morphology and significantly improved the heat distortion temperature (HDT) of the PLA matrix. Binding energies results indicate that low M_w of PEG with GO has excellent compatibility. Dispersed morphologies of the hybrid GO/PEG show that the dynamic impregnating had stronger blending capacity than the internal mixing and obviously improved the exfoliated morphology of GO in the PLA. Crystallization behaviors indicate that the hybrid GO/PEG with the low M_w of PEG based on dynamic impregnating effectively enhanced the crystallinity of PLA, and the cold crystallization character of PLA disappeared in the melting process. Moreover, the storage modulus and loss factor of the PLA-based composites were also investigated and their HDT was improved with the introduction of hybrid GO/PEG. Furthermore, a physical model for the dispersed morphology of the hybrid GO/PEG in the PLA matrix was established. Overall, the unique blending technique of hybrid GO/PEG via dynamic impregnating is an effective approach to enhance the property range of PLA and is suitable for many industrial applications. Full article

The electrical conductivity of extrinsically conducting polymer composite systems passes through a transition state known as percolation threshold. A discussion has been made on how different Sigmoidal models (S-models), such as Sigmoidal–Boltzmann (SB), Sigmoidal–Dose Response (SD), Sigmoidal–Hill (SH), Sigmoidal–Logistic (SL), and Sigmoidal–Logistic-1 (SL-1), can be applied to predict the percolation threshold of electrical conductivity for ethylene vinyl acetate copolymer (EVA) and acrylonitrile butadiene copolymer (NBR) conducting composite systems filled with different carbon fillers. An interesting finding that comes from these observations is that the percolation threshold for electrical conductivity determined by SB and SD models are similar, whereas, the other models give different result when estimated for a particular composite system. This similarity and discrepancy in the results of percolation threshold have been discussed by considering the strength, weakness, and limitation of the models. The percolation threshold value for the composites has also been determined using the classical percolation theory and compared with the sigmoidal models. Moreover, to check the universal applicability, these Sigmoidal models have also been tested on results from some published literature. Finally, it is revealed that, except SL-1 model, the remaining models can successfully be used to determine the percolation threshold of electrical conductivity for extrinsically conductive polymer composites. Full article

Lipid membranes can incorporate amphiphilic or polyphilic molecules leading to specific functionalities and to adaptable properties of the lipid bilayer host. The insertion of guest molecules into membranes frequently induces changes in the shape of the lipid matrix that can be visualized by transmission electron microscopy (TEM) techniques. Here, we review the use of stained and vitrified specimens in (cryo)TEM to characterize the morphology of amphiphilic and polyphilic molecules upon insertion into phospholipid model membranes. Special emphasis is placed on the impact of novel synthetic amphiphilic and polyphilic bolalipids and polymers on membrane integrity and shape stability. Full article

A facile cellulose solvent 1,3-diallyl-2-ethylimidazolium acetate ([AAeim][OAc]) with high electrical conductivity has been designed and synthesized for the first time, via a quaternization reaction and ion exchange method. The dissolution characteristics of cellulose in this solvent were studied in detail. Meanwhile, the co-solvent system was designed by adding an aprotic polar solvent dimethyl sulfoxide (DMSO) in [AAeim][OAc]. The effects of temperature and the mass ratio of DMSO to [AAeim][OAc] on the solubility of cellulose were studied. Furthermore, the effects of regeneration on the molecular structure and thermal stability of cellulose were determined by Fourier transform infrared spectroscopy (FT-IR), thermal gravity analysis (TGA) and X-ray diffraction (XRD). The findings revealed that the synthesized ionic liquid (IL) has a relatively low viscosity, high conductivity and a good dissolving capacity for bamboo dissolving pulp cellulose (Degree of Polymerization: DP = 650). The macromolecular chain of the cellulose is less damaged during the dissolution and regeneration process. Due to the increased number of “free” anions [OAc]⁻ and cations [AAeim]⁺, the addition of DMSO can significantly increase the solubility of the cellulose up to 12 wt % at the mass ratio of 3:1, indicating that the synthesized IL has a potential application in the electrospinning field. Full article

Solvent vapor annealing of block copolymer (BCP) thin films can produce a range of interesting morphologies, especially when the perpendicular orientation of micro-domains with respect to the substrate plays a role. This, for instance, allows BCP thin films to serve as useful templates for nanolithography and hybrid materials preparation. However, precise control of the arising morphologies is essential, but in most cases difficult to achieve. In this work, we investigated the solvent and thickness effects on the morphology of poly(styrene-b-2 vinyl pyridine) (PS-b-P2VP) thin films with a film thickness range from 0.4 L₀ up to 0.8 L₀. Ordered perpendicular structures were achieved. One of the main merits of our work is that the phase behavior of the ultra-high molecular weight BCP thin films, which hold a 100-nm sized domain distance, can be easily monitored via current available techniques, such as scanning electron microscope (SEM), atomic force microscope (AFM), and transmission electron microscope (TEM). Systematic monitoring of the self-assembly behavior during solvent vapor annealing can thus provide an experimental guideline for the optimization of processing conditions of related BCP films systems. Full article

Antibacterial metalized poly(vinylidene fluoride) (PVDF) porous membranes with a nano-layer were obtained via the method of vapor-induced phase separation combined with magnetron sputtering of copper. Magnetron sputtering has such advantages as high deposition rates, low substrate temperatures, and good adhesion of films on substrates. The influence brought by deposition time on the microstructure, hydrophobic property, copper distribution state, anti-biofouling, and permeation separation performance was investigated via atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX) spectrometry, contact angle measurements, and capillary flow porometry, along with the porosity, water flux, protein solution flux, rejection rate, water flux recovery rate, and antibacterial property. The results showed that copper particles formed island-type deposits on the membrane surface and were embedded into cross-section pores near the surface owning to the interconnection of pores. Subsequently, the water flux and protein solution flux declined, but the rejection rate and water flux recovery rate increased. Meanwhile, Cu-coated PVDF membranes exhibited an excellent antibacterial ability. Full article

The main motivation for development of biobased polymers was their biodegradability, which is becoming important due to strong public concern about waste. Reflecting recent changes in the polymer industry, the sustainability of biobased polymers allows them to be used for general and engineering applications. This expansion is driven by the remarkable progress in the processes for refining biomass feedstocks to produce biobased building blocks that allow biobased polymers to have more versatile and adaptable polymer chemical structures and to achieve target properties and functionalities. In this review, biobased polymers are categorized as those that are: (1) upgrades from biodegradable polylactides (PLA), polyhydroxyalkanoates (PHAs), and others; (2) analogous to petroleum-derived polymers such as bio-poly(ethylene terephthalate) (bio-PET); and (3) new biobased polymers such as poly(ethylene 2,5-furandicarboxylate) (PEF). The recent developments and progresses concerning biobased polymers are described, and important technical aspects of those polymers are introduced. Additionally, the recent scientific achievements regarding high-spec engineering-grade biobased polymers are presented. Full article

In this work, polyamide 11 (PA11) and stone ground wood fibres (SGW) were used, as an alternative to non-bio-based polymer matrices and reinforcements, to obtain short fibre reinforced composites. The impact of the reinforcement on the thermal degradation, thermal transitions and microstructure of PA11-based composites were studied. Natural fibres have lower degradation temperatures than PA11, thus, composites showed lower onset degradation temperatures than PA11, as well. The thermal transition and the semi-crystalline structure of the composites were similar to PA11. On the other hand, when SGW was submitted to an annealing treatment, the composites prepared with these fibres increased its crystallinity, with increasing fibre contents, compared to PA11. The differences between the glass transition temperatures of annealed and untreated composites decreased with the fibre contents. Thus, the fibres had a higher impact in the composites mechanical behaviour than on the mobility of the amorphous phase. The crystalline structure of PA11 and PA11-SGW composites, after annealing, was transformed to α’ more stable phase, without any negative impact on the properties of the fibres. Full article

This paper reviews the development of new high-temperature polymeric materials applicable to plastic substrates in image display devices with a focus on our previous results. Novel solution-processable colorless polyimides (PIs) with ultra-low linear coefficients of thermal expansion (CTE) are proposed in this paper. First, the principles of the coloration of PI films are briefly discussed, including the influence of the processing conditions on the film coloration, as well as the chemical and physical factors dominating the low CTE characteristics of the resultant PI films to clarify the challenges in simultaneously achieving excellent optical transparency, a very high T_g, a very low CTE, and excellent film toughness. A possible approach of achieving these target properties is to use semi-cycloaliphatic PI systems consisting of linear chain structures. However, semi-cycloaliphatic PIs obtained using cycloaliphatic diamines suffer various problems during precursor polymerization, cyclodehydration (imidization), and film preparation. In particular, when using trans-1,4-cyclohexanediamine (t-CHDA) as the cycloaliphatic diamine, a serious problem emerges: salt formation in the initial stages of the precursor polymerization, which terminates the polymerization in some cases or significantly extends the reaction period. The system derived from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and t-CHDA can be polymerized by a controlled heating method and leads to a PI film with relatively good properties, i.e., excellent light transmittance at 400 nm (T₄₀₀ = ~80%), a high T_g (>300 °C), and a very low CTE (10 ppm·K⁻¹). However, this PI film is somewhat brittle (the maximum elongation at break, ε_{b max} is about 10%). On the other hand, the combination of cycloaliphatic tetracarboxylic dianhydrides and aromatic diamines does not result in salt formation. The steric structures of cycloaliphatic tetracarboxylic dianhydrides significantly influence the polymerizability with aromatic diamines and the CTE values of the resultant PI films. For three isomers of hydrogenated pyromellitic dianhydride, the steric structure effect on the polymerizability and the properties of the PI films is discussed. 1,2,3,4-Cyclobutanetetracarboxylic dianhydride (CBDA) is a very unusual cycloaliphatic tetracarboxylic dianhydride that is suitable for reducing the CTE. For example, the PI system derived from CBDA and 2,2′-bis(trifluoromethyl)benzidine (TFMB) yields a colorless PI film with a relatively low CTE (21 ppm·K⁻¹). However, this PI is insoluble in common organic solvents, which means that it is neither solution-processable nor compatible with the chemical imidization process; furthermore, the film is somewhat brittle (ε_b < 10%). In addition, the effect of the film preparation route on the film properties is shown to be significant. Films prepared via chemical imidization always have higher optical transparency and lower CTE values than those prepared via the conventional two-step process (i.e., precursor casting and successive thermal imidization). These results suggest that compatibility with the chemical imidization process is the key for achieving our goal. To dramatically improve the solubility in the CBDA-based PI systems, a novel amide-containing aromatic diamine (AB-TFMB), which possesses the structural features of TFMB and 4,4′-diaminobenzanilide (DABA), is proposed. The CBDA(70);6FDA(30)/AB-TFMB copolymer has an ultra-low CTE (7.3 ppm·K⁻¹), excellent optical transparency (T₄₀₀ = 80.6%, yellowness index (YI) = 2.5, and haze = 1.5%), a very high T_g (329 °C), sufficient ductility (ε_{b max} > 30%), and good solution-processability. Therefore, this copolymer is a promising candidate for use as a novel coating-type plastic substrate material. This paper also discusses how the target properties can be achieved without the help of cycloaliphatic monomers. Thus, elaborate molecular design allows the preparation of highly transparent and low-CTE aromatic poly(amide imide) and poly(ester imide) systems. Full article

This paper presents one of the soft computing methods, specifically the artificial neural network technique, that has been used to model the temperature dependence of dynamic mechanical properties and visco-elastic behavior of widely exploited thermoplastic polyurethane over the wide range of temperatures. It is very complex and commonly a highly non-linear problem with no easy analytical methods to predict them directly and accurately in practice. Variations of the storage modulus, loss modulus, and the damping factor with temperature were obtained from the dynamic mechanical analysis tests across transition temperatures at constant single frequency of dynamic mechanical loading. Based on dynamic mechanical analysis experiments, temperature dependent values of both dynamic moduli and damping factor were calculated by three models of well-trained multi-layer feed-forward back-propagation artificial neural network. The excellent agreement between the modeled and experimental data has been found over the entire investigated temperature interval, including all of the observed relaxation transitions. The multi-layer feed-forward back-propagation artificial neural network has been confirmed to be a very effective artificial intelligence tool for the modeling of dynamic mechanical properties and for the prediction of visco-elastic behavior of tested thermoplastic polyurethane in the whole temperature range of its service life. Full article