Shear-Induced Crystallization of Star and Linear Poly(L-lactide)s.

The influence of macromolecular architecture on shear-induced crystallization of poly(L-lactide) (PLLA) was studied. To this aim, three star PLLAs, 6-arm with Mw of 120 and 245 kg/mol, 4-arm with Mw of 123 kg/mol, and three linear PLLAs with Mw of 121, 240 and 339 kg/mol, were synthesized and examined. The PLLAs were sheared at 170 and 150 °C, at 5/s, 10/s and 20/s for 20 s, 10 s and 5 s, respectively, and then cooled at 10 or 30 °C/min. Shear-induced crystallization during cooling was followed by a light depolarization method, whereas the crystallized specimens were examined by DSC, 2D-WAXS, 2D-SAXS and SEM. The effect of shear depended on the shearing conditions, cooling rate and polymer molar mass but it was also affected by the macromolecular architecture. The shear-induced crystallization of linear PLLA with Mw of 240 kg/mol was more intense than that of the 6-arm polymer with similar Mw, most possibly due to its higher Mz. However, the influence of shear on the crystallization of the star polymers with Mw close to 120 kg/mol was stronger than on that of their linear analog. This was reflected in higher crystallization temperature, as well as crystallinity achieved during cooling.

Modification of Polylactide Nonwovens with Carbon Nanotubes and Ladder Poly(silsesquioxane).

Electrospun nonwovens of poly(L-lactide) (PLLA) modified with multiwall carbon nanotubes (MWCNT) and linear ladder-like poly(silsesquioxane) with methoxycarbonyl side groups (LPSQ-COOMe) were obtained. MWCNT and LPSQ-COOMe were added to the polymer solution before the electrospinning. In addition, nonwovens of PLLA grafted to modified MWCNT were electrospun. All modified nonwovens exhibited higher tensile strength than the neat PLA nonwoven. The addition of 10 wt.% of LPSQ-COOMe and 0.1 wt.% of MWCNT to PLLA increased the tensile strength of the nonwovens 2.4 times, improving also the elongation at the maximum stress.

Structure and Mechanical Properties of iPP-Based Nanocomposites Crystallized under High Pressure.

The unique nonparallel chain arrangement in the orthorhombic γ-form lamellae of isotactic polypropylene (iPP) results in the enhancement of the mechanical properties of γ-iPP. Our study aimed at the investigation of the mechanical properties of γ-iPP nanocomposites with 1-5 wt.% multiwall carbon nanotubes (MWCNT) and 5 wt.% organo-modified montmorillonite prepared by melt-mixing and high-pressure crystallization. Neat iPP and the nanocomposites were crystallized under high pressures of 200 MPa and 300 MPa, and for comparison under 1.4 MPa, in a custom-built high-pressure cell. The structure of the materials was studied using WAXS, SAXS, DSC, and SEM, whereas their mechanical properties were tested in plane-strain compression. Under a small pressure of 1.4 MPa, polymer matrix in all materials crystallized predominantly in the α-form, the most common monoclinic form of iPP, whereas under high pressure it crystallized in the γ-form. This caused a significant increase in the elastic modulus, yield stress, and stress at break. Moreover, due to the presence of MWCNT, these parameters of the nanocomposites exceeded those of the neat polymer. As a result, a 60-70% increase in the elastic modulus, yield stress, and stress at break was achieved by filling of iPP with MWCNT and high-pressure crystallization.

Electrical Conductivity and Antibacterial Activity of Woven Fabrics through Quercetin-Assisted Thermal Reduction of a Graphene Oxide Coating.

Cotton and poly(ethylene terephthalate) (PET) woven fabrics were coated with graphene oxide (GO) using a padding method and the GO deposited on the fiber surfaces was thermally reduced to impart electrical conductivity to the fabrics. To assist the thermal reduction of GO, quercetin (Q)-a natural flavonoid-was used. To this end, before the reduction, the GO-padded fabrics were immersed in Q solutions in ethanol with different Q concentrations. Q enhanced the thermal reduction of GO. Depending on the Q concentration in the solutions, electrical surface resistivities of the cotton fabric of 750 kΩ/sq to 3.3 MΩ/sq and of the PET fabric of 240 kΩ/sq to 730 kΩ/sq were achieved. The cotton and PET fabrics also became hydrophobic, with water contact angles of 163° and 147°, respectively. In addition to the electrical conductivity, the presence of Q resulted in antibacterial activity of the fabrics against Escherichia coli and Staphylococcus aureus.

Electrically conductive crystalline polylactide nonwovens obtained by electrospinning and modification with multiwall carbon nanotubes.

Polylactide nonwovens were electrospun from solutions and then crystallized, one in α-form, and another, S-PLA, made of poly(l-lactide) and poly(d-lactide) 1:1 blend, in scPLA crystals with high melting temperature, close to 220 °C. To make the nonwovens electrically conductive, they were coated with multiwall carbon nanotubes (MWCNT) by padding and dip-coating with an aqueous dispersion of MWCNT. The electrical conductivity evidenced the formation of the electrically conductive MWCNT network on the fiber surfaces. Depending on the coating method, the surface resistivity (Rs) of S-PLA nonwoven of 1.0 kΩ/sq and 0.09 kΩ/sq was reached. To study the effect of surface roughness, before the modification the nonwovens were etched with sodium hydroxide, which additionally made them hydrophilic. The effect of etching depended on the coating method and led to an increase or decrease of Rs, in the case of padding or dip-coating, respectively. All MWCNT-modified nonwovens, unetched and etched, were hydrophobic with water contact angles of 138-144°. Scanning electron microscopy corroborated the presence of MWCNT on the fiber surfaces. Impedance spectroscopy confirmed the dominant role of the network of MWCNT direct contacts on the electrical properties of MWCNT-modified nonwovens in a broad frequency range.

Antibacterial Electroconductive Composite Coating of Cotton Fabric.

Graphene oxide (GO) was deposited on a cotton fabric and then thermally reduced to reduced graphene oxide (rGO) with the assistance of L-ascorbic acid. The GO reduction imparted electrical conductivity to the fabric and allowed for electrochemical deposition of Ag° particles using cyclic voltammetry. Only the Ag°/rGO composite coating imparted antibacterial properties to the fabric against Escherichia coli and Staphylococcus aureus. Ag°/rGO-modified fibers were free of bacterial film, and bacterial growth inhibition zones around the material specimens were found. Moreover, Ag°/rGO-modified fabric became superhydrophobic with WCA of 161°.

Formation of UHMWPE Nanofibers during Solid-State Deformation.

A network of nanofibers is formed in situ through solid-state deformation of disentangled ultra-high molecular weight polyethylene (dis-UHMWPE) during compounding with a polyolefin elastomer below the melting temperature of dis-UHMWPE crystals. Dis-UHMWPE was prepared in the form of powder particles larger than 50 µm by polymerization at low temperatures, which favored the crystallization and prevention of macromolecules from entangling. Shearing the blend for different durations and at different temperatures affects the extent to which the grains of dis-UHMWPE powder deform into nanofibers. Disentangled powder particles could deform into a network of nanofibers with diameters between 110 and 340 nm. The nanocomposite can be further sheared for a longer time to decrease the diameter of dis-UHMWPE nanofibers below 40 nm, being still composed of ≈70 wt.% of crystalline and ≈30 wt.% of amorphous components. Subsequently, these thinner fibers begin to melt and fragment because they are thinner and also because the amorphous defects locally decrease the nanofibers' melting temperature, which results in their fragmentation and partial loss of nanofibers. These phenomena limit the thickness of dis-UHMWPE nanofibers, and this explains why prolonged or more intense shearing does not lead to thinner nanofibers of dis-UHMWPE when compounded in a polymeric matrix.

Microbiologically Pure Cotton Fabrics Treated with Tetrabutylammonium OXONE as Mild Disinfection Agent.

The microbiological purity of textiles plays a pivotal role in the use of textiles, especially in hospitals and other medical facilities. Microbiological purity of cotton fabric was achieved by a new disinfection method using tetrabutyloammonium OXONE (TBA-OXONE) before washing. As a result of the disinfection, the cotton fabric became microbiologically pure, despite the markedly decreased washing time with respect to the widely used standard procedure. Shortening of the washing time allowed for significant energy savings. In addition, the effect of the number of disinfection and washing cycles on the tensile properties and tearing force of the fabric was examined. After 120 disinfection and washing cycles the mechanical properties of cotton fabric were only slightly worsened.

Crystallization of Isotactic Polypropylene Nanocomposites with Fibrillated Poly(tetrafluoroethylene) under Elevated Pressure.

Nanocomposites of isotactic polypropylene with 1-5 wt.% of fibrillated PTFE (PP/T) were prepared, and their crystallization during cooling under elevated pressure, in a wide pressure range, up to 300 MPa, as well as the resulting structure, were examined. The crystallization peak temperatures of PP/T, especially with 3 and 5 wt.% of PTFE, exceeded by up to 13 °C those of neat PP. Moreover, a fine-grain structure was formed in PP/T in the entire pressure range, which proved the ability of the fibrillated PTFE to nucleate crystallization of PP in the γ-form under elevated pressure. This also resulted in a higher crystallinity level developed in the γ-domain, before the temperature range of the α-domain was reached during cooling. Hence, the γ-content increased in comparison to that in neat PP, under the pressure up to 200 MPa, especially under 50-100 MPa.

High-Pressure Crystallization of iPP Nucleated with 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol.

1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) is highly effective in nucleation of the α- form of isotactic polypropylene (iPP). However, its role in high-pressure crystallization of iPP, facilitating the formation of the γ- polymorph, has not been explored. The present paper focuses on the influence of DMDBS on nucleation of high-pressure crystallization of iPP. iPP with 0.2-1.0 wt.% of the DMDBS was crystallized under elevated pressure, up to 300 MPa, in various thermal conditions, and then analyzed by PLM, WAXD, SEM, and DSC. During cooling, crystallization temperatures (Tc) were determined. It was found that under high-pressure DMDBS nucleated crystallization of iPP in the orthorhombic γ- form. As a consequence, Tc and the γ- form content increased for the nucleated iPP, while the size of polycrystalline aggregates decreased, although the effects depended on DMDBS content. The significant increase of Tc and the decrease of grain size under high pressure of 200-300 MPa required higher content of DMDBS than the nucleation of the α-form under lower pressure, possibly due to the effect of pressure on crystallization of DMDBS itself, which is a prerequisite for its nucleating activity.

Phase Structure and Properties of Ternary Polylactide/Poly(methyl methacrylate)/Polysilsesquioxane Blends.

Ternary blends of polylactide (PLA, 90 wt.%) and poly(methyl methacrylate) (PMMA, 10 wt.%) with functionalized polysilsesquioxanes (LPSQ-R) were obtained by solution blending. R groups in LPSQ containing hydroxyethyl (LPSQ-OH), methylglycolic (LPSQ-COOMe) and pentafluorophenyl (LPSQ-F5) moieties of different chemical properties were designed to modify PLA blends with PMMA. The effect of the type of LPSQ-R and their content, 1-3 wt.%, on the structure of the blends was studied with scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (SEM-EDS), dynamic mechanical thermal analysis (DMTA) and Raman spectroscopy. Differential scanning calorimetry (DSC) and tensile tests also showed various effects of LPSQ-R on the thermal and mechanical properties of the blends. Depth-sensing indentation was used to resolve spatially the micro- and nano-scale mechanical properties (hardness and elastic behaviour) of the blends. The results showed clearly that LPSQ-R modulate the structure and properties of the blends.

PLA/ß-CD-based fibres loaded with quercetin as potential antibacterial dressing materials.

Microbial infections lead to elevated inflammatory responses, which usually result in prolonged and incomplete wound healing. Therefore, there is an increasing demand for biodegradable fibres that are effective against a different range of microorganisms, especially those with antibiotic resistance. Herein, quercetin-(Q)-loaded polylactide-based fibres were developed using the electrospinning technique. Since Q exhibits low chemical stability, we used star-shaped polylactides (PLAs) with a ß-CD core to host Q by inclusion complexation. To enhance the stability of the fibres and additionally entrap the Q between polymeric chains, we adapted supramolecular cross-linking by the stereocomplexation of PLAs with opposite configurations. As a control, we prepared an additional formulation of star-shaped/commercial PLA/Q for the preparation of nonwovens in which the ß-CD moiety was not present. All developed fibres were smooth and continuous, with an average diameter of 37 µm. Although nonwovens did not possess diffusible activity, good antibacterial effects against Staphylococcus aureus (S. aureus), Escherichia coli (E.coli) and Klebsiella pneumoniae (K. pneumoniae) were observed. All these features validate the proposed approach, in which different supramolecular interactions were used to modify the properties of PLA-based fibres and, most importantly, show their great potential usefulness against microbial infections.

Melatonin significantly influences seed germination and seedling growth of Stevia rebaudiana Bertoni.

BACKGROUND: Melatonin (MEL) is a signaling molecule in plants that affects developmental processes during vegetative and reproductive growth. Investigations have proved that exogenously applied MEL also has the potential to improve seed germination and plant development. METHODS: In the present study, seeds of stevia, a species with a very low germination rate, were germinated on an agar gel (AG) containing MEL at various concentrations (5, 20, 100, and 500 µM) in light. Seeds germinated on AG without MEL were used as controls. For the first 24 or 48 h of germination, the seeds were maintained in darkness as a pre-incubation step. Some seeds were not exposed to this pre-incubation step. RESULTS: At concentrations of 20 and 5 µM, MEL significantly improved germination, but only in seeds pre-incubated in darkness for 24 h (p < 0.001). At concentrations of 100 and 500 µM, MEL had an inhibitory effect on germination, regardless of the pre-incubation time. Melatonin also affected plantlet properties. At a concentration of 20 µM, MEL increased plantlet fresh weight and leaf numbers. At a concentration of 5 µM, it promoted plantlet height. Regarding root development, the most favorable MEL concentration was 500 µM. Biochemical analysis revealed that MEL promoted higher pigment concentrations but hampered superoxide dismutase activity. On the other hand, the concentrations of sugars and phenolics, as well as the activities of catalase and peroxidase, increased at a MEL concentration of 500 µM. DISCUSSION: The results suggest that MEL can improve germination of positively photoblastic stevia seeds and that it can play a role in plantlet development. However, the effects observed in the present study depended on the quantity of MEL that was applied.

Novel blends of polylactide with ethylene glycol derivatives of POSS.

Polylactide (PLA), a main biodegradable and biobased candidate for the replacement of petrochemical polymers, is stiff and brittle at room conditions. It is therefore of high interest to formulate new PLA-based materials suitable for applications demanding flexibility and toughness. In this work, novel blends of PLA with polyhedral oligomeric silsesquioxanes (POSS) grafted with longer (P1) and shorter (P2) arms of ethylene glycol derivatives were prepared and studied. It was hypothesized that, owing to their architecture with the central POSS cage grafted with arms, miscibility and stability of the blends could be improved. Indeed, PLA/P1 blends were homogeneous despite P1 relatively high Mw of 9,500 g mol-1. The blend with 20 wt% of P1, having Tg at 16 °C, was transparent and flexible, elastomer-like material with excellent drawability. The blend remained homogeneous and retained its good drawability as well as flexibility during 6 months of aging at room temperature: a 2 % secant modulus of elasticity well below 100 MPa, a low yield stress below 2 MPa, and and a large strain at break of 8 (800 %). Contary to that, PLA/P2 blends were only partially miscible. Nevertheless, owing to the liquid state of the dispersed phase, the blend with 15 wt% of P2 was transparent and ductile, with Tg at 49 °C, a relatively high yield strength of 29 MPa, and a large strain at break of 2.3 (230 %). The toughening mechanism involved the initiation of crazes and facilitation of their propagation by the liquid inclusions via the local plasticization effect.

The role of nucleating agents in high-pressure-induced gamma crystallization in isotactic polypropylene.

Nucleation of the γ-form in isotactic polypropylene (PP) under high pressure was investigated. Three nucleating agents were used to nucleate crystallization of PP under atmospheric pressure: commercial Hyperform HPN-20E from Milliken Chemical, poly(tetrafluoroethylene) particles nucleating the α-form, and calcium pimelate nucleating the ß-form. Crystallization of neat PP and PP with addition of 0.2 wt% of the nucleating agents was studied. Specimens were either kept at 200 °C under pressure of 200 MPa for time ranging from 2 min to 4 h or for 15 min under pressure ranging from 1.3 to 300 MPa. After cooling to ambient temperature and releasing the pressure, the specimens were analyzed by DSC, WAXD, and PLM to have an insight into the structure and to determine a crystallinity level and contents of crystallographic forms. Both α-nucleating agents strongly nucleated crystallization of PP under high pressure in the γ-form, whereas the ß-nucleating agent had only a slight effect. The results show the possibility to use nucleating agents to nucleate the γ-form of PP under high pressure.

High-pressure crystallization of isotactic polypropylene droplets.

Dispersions of isotactic polypropylene (PP) particles in polystyrene (PS) were produced by interfacially driven breakup of nanolayers in multilayered systems that were fabricated by means of layer-multiplying coextrusion. The droplet size was controlled by the individual PP layer thickness ranging from 12 to 200 nm. In addition, PP was melt blended with PS to produce PP droplets larger than those formed by breakup of nanolayers. The dispersions of PP particles in the PS matrix were melted and annealed under high pressure of 200 MPa. Only the largest PP droplets, with average sizes of 170 µm, crystallized predominantly in the γ form. In the 42-µm droplets obtained by breakup of 200 nm layers, a minor content of the γ form was found whereas the smaller droplets obtained by breakup of the thinner nanolayers contained the α form and/or the mesophase. The results showed that the γ phase formed only in the droplets sufficiently large to contain the most active heterogeneities nucleating PP crystallization under atmospheric pressure. It is concluded that the presence of nucleating heterogeneities is necessary for crystallization of PP in the γ form under high pressure.

Mechanical and thermal properties of green polylactide composites with natural fillers.

Green composites of PLA with micropowders derived from agricultural by-products such as oat husks, cocoa shells, and apple solids that remain after pressing have been prepared by melt mixing. The thermal and mechanical properties of the composites, including the effect of matrix crystallization and plasticization with poly(propylene glycol), have been studied. All fillers nucleated PLA crystallization and decreased the cold-crystallization temperature. They also affected the mechanical properties of the compositions, increasing the modulus of elasticity but decreasing the elongation at break and tensile impact strength although with few exceptions. Plasticization of the PLA matrix improved the ductility of the composites.