Hydrogen Bonded Dimer of an Alcohol with the Derived Carboxylic Acid Triggering their Sorption by Nanoporous-crystalline PPO Films.

Films exhibiting nanoporous-crystalline (NC) phases of poly(2,6-dimethyl-1,4-phenylene) oxide (PPO), which are highly effective to absorb apolar organic guest molecules, are also able to absorb polar molecules (like alcohols and carboxylic acids) but only from concentrated organic solutions. NC PPO films, which do not absorb alcohols and carboxylic acids from diluted aqueous solutions, exhibits a huge uptake (even above 30 wt %) of benzyl alcohol (BAL) and benzoic acid (BA), if BA is obtained by spontaneous room temperature oxidation of BAL in aqueous solution. This phenomenon is rationalized by an easy uptake, mainly by the PPO intrahelical crystalline empty channels, of a BAL/BA 1/1 hydrogen-bonded dimer. This huge uptake of BAL/BA dimer by NC PPO films, which is also fast for films exhibiting the orientation of the crystalline helices perpendicular to the film plane (c⊥ orientation), can be exploited for purification of water from BAL, when present in traces. High and fast sorption of a hydrogen bonded dimer and negligible sorption of the two separate compounds is possibly unprecedented for absorbent materials.

Dependence on Film Thickness of Guest-Induced c Perpendicular Orientation in PPO Films.

For poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films exhibiting nanoporous-crystalline (NC) phases, c⟂ orientation (i.e., crystalline polymer chain axes being preferentially perpendicular to the film plane) is obtained by crystallization of amorphous films, as induced by sorption of suitable low-molecular-mass guest molecules. The occurrence of c⟂ orientation is relevant for applications of NC PPO films because it markedly increases film transparency as well as guest diffusivity. Surprisingly, we show that the known crystallization procedures lead to c⟂ oriented thick (50-300 µm) films and to unoriented thin (≤20 µm) films. This absence of crystalline phase orientation for thin films is rationalized by fast guest sorption kinetics, which avoid co-crystallization in confined spaces and hence inhibit formation of flat-on lamellae. For thick films exhibiting c⟂ orientation, sigmoid kinetics of guest sorption and of thickening of PPO films are observed, with inflection points associated with guest-induced film plasticization. Corresponding crystallization kinetics are linear with time and show that co-crystal growth is poorly affected by film plasticization. An additional relevant result of this study is the linear relationship between WAXD crystallinity index and DSC melting enthalpy, which allows evaluation of melting enthalpy of the NC α form of PPO (ΔHmο = 42 ± 2 J/g).

c-Perpendicular Orientation of Poly(ʟ-lactide) Films.

Poly(ʟ-lactide) (PLLA) films, even of high thickness, exhibiting co-crystalline and crystalline α phases with their chain axes preferentially perpendicular to the film plane (c⊥ orientation) have been obtained. This c⊥ orientation, unprecedented for PLLA films, can be achieved by the crystallization of amorphous films as induced by low-temperature sorption of molecules being suitable as guests of PLLA co-crystalline forms, such as N,N-dimethylformamide, cyclopentanone or 1,3-dioxolane. This kind of orientation is shown and quantified by two-dimensional wide-angle X-ray diffraction (2D-WAXD) patterns, as taken with the X-ray beam parallel to the film plane (EDGE patterns), which present all the hk0 arcs centered on the meridian. PLLA α-form films, as obtained by low-temperature guest-induced crystallization, also exhibit high transparency, being not far from those of the starting amorphous films.

Molecular Features Behind Formation of α or ß Co-Crystalline and Nanoporous-Crystalline Phases of PPO.

Guest molecular features determining the formation of α and ß phases of poly(2-6-dimethyl-1,4-phenylene) oxide (PPO) are explored by collecting literature data and adding many new film preparations, both by solution casting and by guest sorption in amorphous films. Independently of the considered preparation method, the α-form is favored by the hydrophobic and bulky guest molecules, while the hydrophilic and small guest molecules favor the ß-form. Furthermore, molecular modeling studies indicate that the ß-form inducer guests establish stronger dispersive interactions with the PPO units than the α-form inducer guests. Thus, the achievement of co-crystalline (and derived nanoporous crystalline) α- and ß-forms would result from differences in energy gain due to the host-guest interactions established at the local scale.

Nanoporous Crystalline Composite Aerogels with Reduced Graphene Oxide.

High-porosity monolithic composite aerogels of syndiotactic polystyrene (sPS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) containing reduced graphene oxide (r-GO) were prepared and characterized. The composite aerogels obtained by supercritical carbon dioxide (scCO2) extraction of sPS/r-GO and PPO/r-GO gels were characterized by a fibrillar morphology, which ensured good handling properties. The polymer nanoporous crystalline phases obtained within the aerogels led to high surface areas with values up to 440 m2 g-1. The role of r-GO in aerogels was studied in terms of catalytic activity by exploring the oxidation capacity of composite PPO and sPS aerogels toward benzyl alcohol in diluted aqueous solutions. The results showed that, unlike sPS/r-GO aerogels, PPO/r-GO aerogels were capable of absorbing benzyl alcohol from the diluted solutions, and that oxidation of c.a. 50% of the sorbed benzyl alcohol molecules into benzoic acid occurred.

Axial Orientation of Co-Crystalline Phases of Poly(2,6-Dimethyl-1,4-Phenylene)Oxide Films.

Films exhibiting co-crystalline (CC) phases between a polymer host and low-molecular-mass guest molecules are relevant for many applications. As is usual for semi-crystalline polymers, axially oriented films can give relevant information on the crystalline structure, both by Wide Angle X-ray diffraction fiber patterns and by polarized Fourier-transform infrared spectroscopy. Axially oriented CC phases of poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) with 1,3,5-trimethylbenzene (mesitylene) can be simply obtained by the stretching of CC PPO films. In fact, due to the plasticization effect of this highly boiling guest, PPO orientation can occur in a stretching temperature range (170-175 °C) nearly 50 °C lower than that generally needed for PPO films (220-230 °C). This low stretching temperature range allows avoidance of polymer oxidation, as well as formation of the mesomorphic dense γ PPO phase. Axially oriented CC phases of PPO with toluene, i.e., with a more volatile guest, can be instead obtained by the stretching (in the same low temperature range: 170-175 °C) of CC PPO blend films with polystyrene.

Sustainable in Situ Approach to Covalently Functionalize Graphene Oxide with POSS Molecules Possessing Extremely Low Dielectric Behavior.

Incorporation of multifunctional inorganic additives into the commercial polymers still stands as the most captivating and effective way to realize new-generation electronic components. Here, we introduce a simple, cost-effective, and environmentally benign method to covalently functionalize graphene oxide (GO) with vinyl- and aminopropyl-functionalized hybrid silica spheres with a polyhedral oligomeric silsesquioxane (POSS)-siloxane composition. The reaction has been carried out in a mixture of ethanol and water (used as a medium) at ambient conditions with silane precursors. Later, the synthesized hybrid material has been tested for its dielectric properties after blending with syndiotactic polystyrene, a commercially available insulating semicrystalline polymer. It was observed that the dielectric constant decreases with the addition of GOPOSS up to 1.85 with a dielectric loss of 0.02 at 5 GHz. Significant improvements in the thermal properties of the composites were verified with minimal filler loading.

Influence of Boron Nitride Nanosheets on the Crystallization and Polymorphism of Poly(l-lactide).

This work reports on the impact of delaminated boron nitride nanosheets (BNNSs) on the crystallization behavior and crystalline structure of melt-crystallized poly-L-lactic acid (PLLA). Wide-angle X-ray diffraction and scanning electron microscopy data revealed that the addition of lower loadings of BNNSs (∼0.5 wt %) resulted in the highly dispersed PLLA nanocomposites, whereas the higher loading of BNNSs (≥1 wt %) leads to the agglomerated nanocomposites. It is shown that the presence of lower loadings of the BNNSs (∼0.5 wt %) induces the formation of ordered α form when crystallizing from the melt at a cooling rate of 10 °C/min, but the mixture of α' and α forms is formed in the presence of higher loading of BNNSs (≥1 wt %). Polarized optical microscopy images revealed that the crystallization rate of PLLA was significantly enhanced in the presence of lower loading of BNNSs (∼0.5 wt %) as corroborated by the increasing number of tiny spherulites. The strong interaction between the highly dispersed BNNSs and PLLA chains induces the conformationally ordered α form, and the various experimental techniques revealed that crystallization of PLLA occurred rapidly with the narrow distribution of crystal size and degree of crystal perfection in highly dispersed nanocomposites. Furthermore, the thermal conductivity of PLLA/BNNSs nanocomposites was found to increase significantly with BNNSs loading.

Polypropylene/Layered Double Hydroxide Nanocomposites: Influence of LDH Intralayer Metal Constituents on the Properties of Polypropylene.

Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (∼50-200 nm). Such delaminated Co-Al LDH, Zn-Al LDH, and Co-Zn-Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T 0.5)) of the iPP nanocomposite containing three-metal LDH (Co-Zn-Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co-Al LDH and Zn-Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co-Zn-Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co-Al LDH (24%) and iPP/Zn-Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.

Screen-Printable Electronic Ink of Ultrathin Boron Nitride Nanosheets.

Two-dimensional materials play a vital role in the current electronic industry in the fabrication of devices. In the present work, we have exfoliated and stabilized the insulating hexagonal boron nitride (hBN) by means of a polymer-assisted liquid-phase technique. Further, the highly viscous ink of hBN was prepared, and its printability on various commercially available substrates was studied. The morphology of the printed patterns reveals the layered arrangement of hBN. The various electrical and dielectric characterizations, carried out on a metal-insulator-metal capacitor, testified its potential applications in various fields of printed electronics.

Syndiotactic Polystyrene/Hybrid Silica Spheres of POSS Siloxane Composites Exhibiting Ultralow Dielectric Constant.

Homogeneously dispersed hybrid silica/syndiotactic polystyrene composites were investigated for low-κ dielectric applications. The composites were prepared by a solution blending method, and their microstructures were analyzed by SEM, TEM, and AFM. Crystallization and phase transformation behavior of sPS were investigated using differential scanning calorimetry and wide-angle X-ray diffraction. These composites exhibited improved thermal stability and reduced thermal expansion coefficients. Promising dielectric properties were observed for the composites in the microwave frequency region with a dielectric constant (κ = 1.95) and loss (tan δ = 10(-4)) at 5 GHz.

Polypropylene/Layered Double Hydroxide (LDH) Nanocomposites: Influence of LDH Particle Size on the Crystallization Behavior of Polypropylene.

Highly dispersed isotactic polypropylene (iPP) nanocomposites were prepared by incorporating two different sized Mg-Al LDH nanoparticles with different loadings from 1 to 10 wt % using a modified solvent mixing method. Larger sized LDH nanoparticles (∼3-4 µm) were prepared from the gel form of Mg-Al LDH, and the smaller sized nanoparticles (∼50-200 nm) were prepared by sonication of as-synthesized LDH particles. Such obtained LDH nanoparticles were carefully characterized using wide-angle X-ray diffraction (WAXD), transmission electron microscopy, and scanning electron microscopy. WAXD and atomic force microscopy results indicate that the LDH nanoparticles were highly dispersed in the iPP matrix. The influence of LDH nanoparticles size and concentration on the thermal stability, spherulitic morphology, melting behavior, isothermal crystallization kinetics, and lamellar structure of iPP were investigated. Incorporation of low loadings of sonicated LDH particles (e.g., 1-2.5 wt %) show substantial effect on thermal stability, spherulite size, crystallinity, and crystallization half-time and lamellar morphology of iPP compared to the pure iPP and that of nanocomposites with larger LDH particles with same loadings. The better nucleation ability of iPP in the presence of sonicated LDH can be attributed to the high surface area of LDH nanoparticles along with its better dispersibility within the polymer matrix. The incorporation of LDH nanoparticles does not change the crystallization growth mechanism and crystal structure of iPP.