Manuel De Guzman

Preparation and Characterization of Bioplastic-Based Green Renewable Composites from Tapioca with Acetyl Tributyl Citrate as a Plasticizer

Granular tapioca was thermally blended with poly(lactic acid) (PLA). All blends were prepared using a plasti-corder and characterized for tensile properties, thermal properties and morphology. Scanning electron micrographs showed that phase separation occurred, leading to poor tensile properties. Therefore, methylenediphenyl diisocyanate (MDI) was used as an interfacial compatibilizer to improve the mechanical properties of PLA/tapioca blends. The addition of MDI could improve the tensile strength of the blend with 60 wt% tapioca, from 19.8 to 42.6 MPa. In addition, because PLA lacked toughness, acetyl tributyl citrate (ATBC) was added as a plasticizer to improve the ductility of PLA. A significant decrease in the melting point and glass-transition temperature was observed on the basis of differential scanning calorimetry, which indicated that the PLA structure was not dense after ATBC was added. As such, the brittleness was improved, and the elongation at break was extended to several hundred percent. Therefore, mixing ATBC with PLA/tapioca/MDI blends did exhibit the effect of plasticization and biodegradation. The results also revealed that excessive plasticizer would cause the migration of ATBC and decrease the tensile properties.

Multilayered poly(vinylidene fluoride) composite membranes with improved interfacial compatibility: correlating pervaporation performance with free volume properties.

A spin-coating process integrated with an ozone-induced graft polymerization technique was applied in this study. The purpose was to improve the poor interfacial compatibility between a selective layer of poly(2-hydroxyethyl methacrylate) (PHEMA) and the surface of a poly(vinylidene fluoride) (PVDF) substrate. The composite membranes thus fabricated were tested for their pervaporation performance in dehydrating an ethyl acetate/water mixture. Furthermore, the composite membranes were characterized by field emission scanning electron microscopy (FE-SEM) for morphological change observation and by Fourier transform infrared spectroscopy equipped with attenuated total reflectance (ATR-FTIR) for surface chemical composition analysis. Effects of grafting density and spin-coating speed on pervaporation performance were examined. The composite membrane pervaporation performance was elucidated by means of free volume and depth profile data obtained with the use of a variable monoenergy slow positron beam (VMSPB). Results indicated that a smaller free volume was correlated with a higher pervaporation performance of a composite membrane consisting of a selective layer of spin-coated PHEMA on a PHEMA-grafted PVDF substrate (S-PHEMA/PHEMA-g-PVDF). The composite membrane depth profile illustrated that an S-PHEMA layer spin-coated at a higher revolutions per minute (rpm) was thinner and denser than that at a lower rpm.

Solving the Charging Effect in Insulating Materials Probed by a Variable Monoenergy Slow Positron Beam

A variable monoenergy slow positron beam (VMSPB) operating at a high vacuum on insulating materials encounters a problem of significant surface charging effect with time. As a result, positronium formation is inhibited, and the positron annihilation radiation counting rate is reduced; these consequently distorted the experimental positron annihilation and results. To solve such problems, a technique of depositing an ultrathin layer of sputtering noble metals on insulators is developed. We report a successful method of sputtering a few atomic layers of platinum (∼1 nm) on a polyamide membrane to completely remove the charging effect for VMSPB applications in insulators.

Synthesis of biodegradable polycaprolactone/polyurethane by curing with H2O

To prepare a pre-polymer in this study, the following materials were used: 4,4′-diphenylmethane diisocyanate, poly(ε-caprolactone) diol (PCL), and polytetramethylene ether glycol. The pre-polymer was then cured using H2O to form a new type of polyurethane (PU), PCL/H2O-PU. Fourier transform infrared analysis confirmed the successful synthesis of PCL/H2O-PU. Results from thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis showed that the thermal resistance and glass transition temperature of PCL/H2O-PU increased with the H2O and the hard segment content. Stress–strain curves for the PCL/H2O-PU specimens showed that with increasing H2O content, the tensile strength and Young’s modulus increased, but the elongation at break decreased. WAXD patterns indicated that with a higher H2O content, the polymer chains were in a more ordered arrangement, although the morphology was still amorphous. The degree of swelling in an aqueous ethanol solution and the hydrolytic degradation rate increased with the PCL content. Scanning electron microscopic images showed that during the degradation period, the original wrinkled surface of PCL/H2O-PU became smooth, and then cracks were formed. The cracks became more severe when the degradation was at a higher temperature.

Effects of surface properties of different substrates on fine structure of plasma-polymerized SiOCH films prepared from hexamethyldisiloxane (HMDSO)

In this study, Doppler broadening energy spectroscopy (DBES) combined with slow positron beam was used to discuss the effect of substrate types on the fine structure of a plasma-polymerized SiOCH layer as a function of depth. From the SEM pictures, the SiOCH films formed on different substrates showed hemispherical macrostructures, and the deposition rate was dependent on the mean pore size. It appears that the morphology of the plasma-polymerized SiOCH films was associated with the porosity-related characteristics of the substrate such as the size/shape of pores. As deposited on the MCE-022 substrate (mixed cellulose esters membrane with a mean pore size of 0.22 μm) with a nodular structure, the SiOCH films had pillar-like structures and high gas permeabilities. DBES results showed that the SiOCH films deposited on different substrates were composed of three layers: the SiOCH bulk layer, the transition layer, and the substrate. It was observed that the microstructure of the SiOCH films was affected layer by layer; a higher surface pore size in the substrates induced thicker transition layers with higher microporosities and led to thinner bulk layers having higher S parameter values during the plasma polymerization. It was also observed that the change in O(2)/N(2) selectivity was consistent with the DBES analysis results. The gas separation performance and DBES analysis results agreed with each other.

Effects of different metals on the synthesis and properties of waterborne polyurethane composites containing pyridyl units

This study used dicyclohexylmethane 4,4-diisocyanate, polybutylene adipate, polyether-1,3-diol, and 2,6-pyridinedimethanol to synthesize a novel water-based polyurethane (WPU) that contained pyridyl units. To enhance the thermal, mechanical, swelling, and antimicrobial properties of the WPU, various metals (silver nitrate, copper acetate, cobalt acetate, and zinc acetate) were incorporated to form WPU/metal composites. In addition, the study investigated the effects of the metal types on the WPU properties. Fourier transform infrared spectroscopy was used to confirm the synthesis of the WPU containing pyridine. Atomic force microscopy illustrated that the added metals increased the WPU surface roughness. The contact angle and degree of swelling tests demonstrated that the added metal reduced the WPU hydrophilicity, and with the addition of other metal types, the hydrophobicity increased considerably. Thermal gravimetric analysis indicated that the initial decomposition temperature of the highest WPU thermal stability was attributed to zinc. In addition, the results of differential scanning calorimetry and dynamic mechanical analysis showed that adding a small amount of metal increased the hard and soft segment glass transition temperatures. A universal strength tester validated that the WPU mechanical properties varied with the different metal additives and that the WPU strength increased. However, the WPU toughness and ductility decreased with the addition of metals; silver provided the highest mechanical strength. An antimicrobial test indicated that silver enhanced the antimicrobial property. The moisture permeability and waterproof property of the WPU coating was also analyzed.

Biocompatibility and characterization of polylactic acid/styrene-ethylene-butylene- styrene composites

Polylactic acid (PLA)/styrene-ethylene-butylene-styrene (SEBS) composites were prepared by melt blending. Differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WXRD) were used to characterize PLA and PLA/SEBS composites in terms of their melting behavior and crystallization. Curves from thermal gravimetric analysis (TGA) illustrated that thermostability increased with SEBS content. Further morphological analysis of PLA/SEBS composites revealed that SEBS molecules were not miscible with PLA molecules in PLA/SEBS composites. The tensile testing for PLA and PLA/SEBS composites showed that the elongation at the break was enhanced, but tensile strength decreased with increasing SEBS content. L929 fibroblast cells were chosen to assess the cytocompatibility; the cell growth of PLA was found to decrease with increasing SEBS content. This study proposes possible reasons for these properties of PLA/SEBS composites.