Development and study of fully biodegradable composite materials based on poly(butylene succinate) and hemp fibers or hemp shives

The use of natural fibers to reinforce polymers is an established practice, and biocomposites have gained an increased interest in areas such as automotive, construction, and agriculture. The purpose of the present work was the preparation and study of fully biodegradable (“green”) composite materials using poly(butylene succinate) (PBSu) as polymeric matrix and hemp fibers and shives as fillers. Composites containing 15, 30, 50, 60, and 70 wt% of fillers were prepared by melt mixing in a twin screw extruder. The composites were studied using Fourier transform infrared spectroscopy, X‐ray diffraction, and differential scanning calorimeter while the dispersion and interfacial adhesion were studied with scanning electron microscopy. From mechanical properties measurements, it was found that tensile and impact strength are both affected by the type and the amount of the used filler. The degree of crystallinity of PBSu was found to decrease by increasing the filler content, although that both fillers can act as nucleating agents. Finally, the degradation rate during enzymatic hydrolysis and soil burial increased in all biocomposites by increasing the filler content. PBSu/hemp shive composites showed higher biodegradation rates than PBSu/hemp fiber composites. POLYM. COMPOS., 37:407–421, 2016. © 2014 Society of Plastics Engineers     

Branched Poly(ε-caprolactone)-Based Copolyesters of Different Architectures and Their Use in the Preparation of Anticancer Drug-Loaded Nanoparticles

Limitations associated with the use of linear biodegradable polyesters in the preparation of anticancer nano-based drug delivery systems (nanoDDS) have turned scientific attention to the utilization of branched-chain (co-)polymers. In this context, the present study evaluates the use of novel branched poly(ε-caprolactone) (PCL)-based copolymers of different architectures for the preparation of anticancer nanoparticle (NP)-based formulations, using paclitaxel (PTX) as a model drug. Specifically, three PCL-polyol branched polyesters, namely, a three-arm copolymer based on glycerol (PCL-GLY), a four-arm copolymer based on pentaerythritol (PCL-PE), and a five-arm copolymer based on xylitol (PCL-XYL), were synthesized via ring-opening polymerization and characterized by proton nuclear magnetic resonance (¹H-NMR), gel permeation chromatography (GPC), intrinsic viscosity, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and Fourier-transform infrared (FT-IR) spectroscopy and cytotoxicity. Then, PTX-loaded NPs were prepared by an oil-in-water emulsion. The size of the obtained NPs varied from 200 to 300 nm, while the drug was dispersed in crystalline form in all formulations. High encapsulation efficiency and high yields were obtained in all cases, while FTIR analysis showed no molecular drug polymer. Finally, in vitro drug release studies showed that the studied nanocarriers significantly enhanced the dissolution rate and extent of the drug.     

Thermomechanical analysis of chain-extended PET and PBT

Two series of samples, one of PET and another of PBT, were received after chain extension at different reaction times with two new chain extenders (diimidodiepoxides). These samples showed different intrinsic viscosity and degree of branching or crosslinking. The effect of this differentiation on thermal properties was studied by thermomechanical analysis (TMA). The parameters studied were the glass transition temperature (T_g), melting temperature (T_m), and the linear expansion coefficient (α). It is remarkable that in the case of PET amorphous or semicrystalline samples, two peaks appeared next to the T_g in the TMA thermogram. The first peak appeared at a temperature very close and lower to the T_g, and the other peak, at higher temperature into the “cold crystallization region.” The presence of two such peaks was not detected in the DSC thermogram of PET samples either in the TMS or DSC thermograms of PBT. The T_g values were found to agree to within ±1°C of those obtained from DSC; on the contrary, the T_m values varied significantly from those received from DSC. The linear expansion coefficient of samples was found to increase with the degree of chain extension. © 1996 John Wiley & Sons, Inc.     

Identification of rheological and structural characteristics of foamable poly(ethylene terephthalate) by reactive extrusion

The reactivity and efficiency of five low molecular weight multifunctional anhydride and epoxy compounds as chemical modifiers of a bottle grade poly(ethylene terephthalate) (PET) resin were evaluated by reactive extrusion under controlled conditions. The two dianhydrides and the three epoxy compounds were used at concentrations based on stoichiometry derived from the measured carboxyl and hydroxyl end group contents of the base resin. Measures of melt viscosity, melt strength, intrinsic viscosity and carboxyl group content were used as criteria of the extent of the modification. Correlations of die pressure with extrudate swell during extrusion, and melt flow index (MFI) with melt strength by off‐line testing of the extrudates permitted the ranking of the modifiers according to their chain‐extending/branching efficiency. For some systems molecular weight increases (related to die pressure/MFI/intrinsic viscosity) accompanied by broadening of the molecular weight distribution (related to die swell/melt strength) were considered excessive. Extrusion foaming experiments with one particular dianhydride modifier that increased the intrinsic viscosity of the resin from 0.71 to 0.9 dl g^?1 indicate that production of low‐density foams by a process involving one‐step reactive modification/gas injection foaming is feasible, at conditions not significantly different from those employed in the simple reactive modification of the PET resin. The rheological and structural parameters determined in this work may be used as criteria to specify PET foamable compositions in terms of types and concentrations of modifiers. Copyright © 2004 Society of Chemical Industry     

Oxidized multiwalled carbon nanotubes as effective reinforcement and thermal stability agents of poly(lactic acid) ligaments

In this study, nanocomposites of poly(lactic acid) (PLA) containing 0.5, 1, and 2.5 wt % oxidized multiwalled carbon nanotubes (MWCNT–COOHs) were prepared by the solved evaporation method. From transmission electron microscopy and scanning electron microscopy micrographs, we observed that the MWCNT–COOHs were well dispersed in the PLA matrix and, additionally, there was increased adhesion between PLA and the nanotubes. As a result, all of the studied nanocomposites exhibited higher mechanical properties than neat PLA; this indicated that the MWCNT–COOHs acted as efficient reinforcing agents, whereas in the nonoxidized multiwalled carbon nanotubes, the mechanical properties were reduced. Nanotubes can act as nucleating agents and, thereby, affect the thermal properties of PLA and, especially, the crystallization rate, which is faster than that of neat PLA. From the thermogravimetric data, we observed that the PLA/MWCNT–COOH nanocomposites presented relatively better thermostability than PLA; this was also verified from the calculation of activation energy. On the contrary, the addition of MWCNT–COOH had a negative effect on the enzymatic hydrolysis rate of PLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of evolved interactions in poly(butylene succinate)/fumed silica biodegradable in situ prepared nanocomposites on molecular weight,material properties,and biodegradability

Poly(butylene succinate) (PBSu)/fumed silica nanocomposites were prepared in situ by condensation polymerization. TEM micrographs verified that the dispersion of the nanoparticles was homogeneous in the PBSu matrix, while some small agglomerates were also formed at a higher SiO₂ content. ¹³C NMR spectra affirmed that the hydroxyl end groups of PBSu could form covalent bonds with the surface silanol groups of SiO₂. These interactions affected the molecular weight of the prepared nanocomposites. At low concentrations the SiO₂ nanoparticles acted as chain extenders, increasing the molecular weight of PBSu, while at higher loadings they resulted in extended branching and crosslinking reactions, leading to gradually decreased molecular weights. Silica nanoparticles acted as nucleating agents, increasing the crystallization rate of PBSu. However, the degree of crystallinity was slightly reduced. Tensile strength and Young's modulus were significantly increased with increasing SiO₂ content. The presence of the nanoparticles resulted in reduced enzymatic hydrolysis rates compared to pure PBSu, attributed to the smaller available organic surface, due to the incorporation of SiO₂, and to the existence of branched and crosslinked macromolecules. Dynamic mechanical and rheological properties were also extensively studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(ethylene terephthalate‐co‐isophthalate)s with low content of isophthalate units

The objective of this work was to study the effect of the introduction of low amounts of isophthalate units on the mechanical properties, crystallization rates, and thermal parameters of poly(ethylene terephthalate). For this reason a series of five random poly(ethylene terephthalate‐co‐isophthalate) copolymers, containing 0.5, 1, 1.5, 2, and 4 mol % isophthalic acid, were prepared by the melt polycondensation process. The intrinsic viscosity of copolymers ranged between 0.7 and 0.8 dL/g. The increase of isophthalate content resulted in a significant decrease of the crystallization rates, but in a small decline of tensile strength, Young's modulus, and elongation at break, whereas tensile strength at yield point remained almost unaffected. Also, a decrease in the melting point was recorded, whereas the glass‐transition temperature was only very slightly affected. The higher decrease for the aforementioned parameters was noted for the copolymer with 4 mol % isophthalate units content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1931–1941, 2002     

Effect of ball milling on the mechanical properties and crystallization of graphene nanoplatelets reinforced short chain branched-polyethylene

Short-chain-branched-polyethylene (SCB-PE) is extensively used in domestic hot and cold piping systems. SCB-PE nanocomposites using graphene nanoplatelets (GNPs) as a filler, were prepared in this work. The effect of ball-milling as a premixing technique prior to melt-mixing, on the crystallization and the nanomechanical properties of the composites has been studied. Two sets of SCB-PE/GNPs nanocomposites with various filler loadings were prepared; one with and one without the ball-milling step. The dispersion of the filler was evaluated by optical microscopy while the crystallization process was studied using differential scanning calorimetry. The nonisothermal crystallization's experimental data were analyzed using various methods. The materials' nanomechanical behavior was investigated by conducting nanoindentation tests. A finite element analysis process was developed to extract the composites' stress–strain behavior. The composites prepared with ball-milling presented improved dispersion of GNPs in the SCB-PE matrix, which affected the crystallization, while nanoindentation tests showed significantly enhanced mechanical properties.