Performance Evaluation of Cellulose Nanofiber with Residual Hemicellulose as a Nanofiller in Polypropylene-Based Nanocomposite.

Residual hemicellulose could enhance cellulose nanofiber (CNF) processing as it impedes the agglomeration of the nanocellulose fibrils and contributes to complete nanofibrillation within a shorter period of time. Its effect on CNF performance as a reinforcement material is unclear, and hence this study seeks to evaluate the performance of CNF in the presence of amorphous hemicellulose as a reinforcement material in a polypropylene (PP) nanocomposite. Two types of CNF were prepared: SHS-CNF, which contained about 11% hemicellulose, and KOH-CNF, with complete hemicellulose removal. Mechanical properties of the PP/SHS-CNF and PP/KOH-CNF showed an almost similar increment in tensile strength (31% and 32%) and flexural strength (28% and 29%) when 3 wt.% of CNF was incorporated in PP, indicating that hemicellulose in SHS-CNF did not affect the mechanical properties of the PP nanocomposite. The crystallinity of both PP/SHS-CNF and PP/KOH-CNF nanocomposites showed an almost similar value at 55-56%. A slight decrement in thermal stability was seen, whereby the decomposition temperature at 10% weight loss (Td10%) of PP/SHS-CNF was 6 °C lower at 381 °C compared to 387 °C for PP/KOH-CNF, which can be explained by the degradation of thermally unstable hemicellulose. The results from this study showed that the presence of some portion of hemicellulose in CNF did not affect the CNF properties, suggesting that complete hemicellulose removal may not be necessary for the preparation of CNF to be used as a reinforcement material in nanocomposites. This will lead to less harsh pretreatment for CNF preparation and, hence, a more sustainable nanocomposite can be produced.

Well-Dispersed Cellulose Nanofiber in Low Density Polyethylene Nanocomposite by Liquid-Assisted Extrusion.

Two different liquid assisted processing methods: internal melt-blending (IMB) and twin-screw extrusion (TWS) were performed to fabricate polyethylene (PE)/cellulose nanofiber (CNF) nanocomposites. The nanocomposites consisted maleic anhydride-grafted PE (PEgMA) as a compatibilizer, with PE/PEgMA/CNF ratio of 97/3/0.5-5 (wt./wt./wt.), respectively. Morphological analysis exhibited that CNF was well-dispersed in nanocomposites prepared by liquid-assisted TWS. Meanwhile, a randomly oriented and agglomerated CNF was observed in the nanocomposites prepared by liquid-assisted IMB. The nanocomposites obtained from liquid-assisted TWS exhibited the best mechanical properties at 3 wt.% CNF addition with an increment in flexural strength by almost 139%, higher than that of liquid-assisted IMB. Results from this study indicated that liquid feeding of CNF assisted the homogenous dispersion of CNF in PE matrix, and the mechanical properties of the nanocomposites were affected by compounding method due to the CNF dispersion and alignment.

Organic Thin Paper of Cellulose Nanofiber/Polyaniline Doped with (±)-10-Camphorsulfonic Acid Nanohybrid and Its Application to Electromagnetic Shielding.

A superior electrical conductivity of 38.5 S/cm and an electromagnetic shielding (EMS) effectiveness of -30 dB (-545 dB/mm) across a wide frequency range of 0-15 GHz, including the X-band, were achieved with thin organic paper of (55 µm) cellulose nanofiber (CNF)/polyaniline (PANI) doped with (±)-10-camphorsulfonic acid nanohybrid. Both electrical conductivity and EMS effectiveness of the PANI-coated CNF were strongly affected by the amount and type of dopant, which could be tunable after fabrication process via simple in situ oxidative polymerization of aniline. Flexible and free-standing film was obtained, since CNF provides good mechanical property without diminishing the electrical property of PANI.

In vitro cytotoxicity of superheated steam hydrolyzed oligo((R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate) and characteristics of its blend with poly(L-lactic acid) for biomaterial applications.

In order to clarify the in vitro cytotoxicity effect of superheated steam (SHS) treated poly((R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate) (PHBHHx) for biomaterial applications, SHS-treated PHBHHx oligoester samples: P(HB-co-6%-HHx) and P(HB-co-11%-HHx) with low and high percentages of unsaturated chain ends were evaluated for their cytotoxicity effects toward the growth of mouse fibroblast cell line NIH 3T3. From the results obtained after 24 and 48 h of the growth test, the SHS-treated PHBHHx oligoesters were found to be nontoxic to the growth of mouse fibroblast NIH 3T3 cell line with cell viability percentages of more than 95%. In order to serve as a potential resorbable medical suture, PHBHHx oligoesters were blended with poly(L-lactic acid) (PLLA) with a weight ratio of PHBHHx oligoester/PLLA = 20:80 (wt/wt) to improve mechanical properties of PHBHHx oligoesters. The PHBHHx oligoesters/PLLA blend films were evaluated for their thermal, mechanical, and surface wetting properties. Thermal properties of the blend films suggested a good compatibility between PHBHHx oligoesters and PLLA components. Mechanical properties of the blend films were determined to be close enough to a desirable strength range of medical sutures. Moreover, contact angle range of 65 < θ < 70° for the blend samples could provide desirable cell adhesion when used as biomaterials. Therefore, the blend of SHS-treated PHBHHx oligoesters and PLLA would be an ideal choice to be used as biomedical materials.

Growth promotion of Spirulina by steelmaking slag: application of solubility diagram to understand its mechanism.

A solubility diagram was employed to understand growth promotion of Arthrospira (Spirulina) platensis by steelmaking slag (SMS). The growth promotion effect of 112 % of freshwater microalga A. platensis was obtained using 5 g/L SMS. However, metabolites, such as pigments, and protein content of A. platensis were not significantly affected. Several metals dissolved in Spirulina-Ogawa-Terui medium were detected by inductively coupled plasma atomic emission spectrometry just after the addition of SMS. The solubility diagram provides information on the chemical speciation of metal elements based on pH and concentration. It is a useful tool to understand the effect of metals on microalgal growth. The metal elements used to control microalgal growth are essential minerals but also act as a source of oxidative stress. Regarding the affecting mechanism of SMS, iron may be the primary element regulating microalgal growth via pathway involving reactive oxygen species, as revealed by superoxide dismutase assay.

Modification of oil palm mesocarp fiber characteristics using superheated steam treatment.

In this study, oil palm mesocarp fiber (OPMF) was treated with superheated steam (SHS) in order to modify its characteristics for biocomposite applications. Treatment was conducted at temperatures 190-230 °C for 1, 2 and 3 h. SHS-treated OPMF was evaluated for its chemical composition, thermal stability, morphology and crystallinity. OPMF treated at 230 °C exhibited lower hemicellulose content (9%) compared to the untreated OPMF (33%). Improved thermal stability of OPMF was found after the SHS treatment. Moreover, SEM and ICP analyses of SHS-treated OPMF showed that silica bodies were removed from OPMF after the SHS treatment. XRD results exhibited that OPMF crystallinity increased after SHS treatment, indicating tougher fiber properties. Hemicellulose removal makes the fiber surface more hydrophobic, whereby silica removal increases the surface roughness of the fiber. Overall, the results obtained herewith suggested that SHS is an effective treatment method for surface modification and subsequently improving the characteristics of the natural fiber. Most importantly, the use of novel, eco-friendly SHS may contribute to the green and sustainable treatment for surface modification of natural fiber.

Characteristic chain-end racemization behavior during photolysis of poly(L-lactic acid).

Photolysis of poly(L-lactic acid) (PLLA) has many unclear points, such as the degradation mechanism, kinetics, products, and racemization mechanism. To clarify these features of PLLA photolysis, we examined the relationship between photolysis and racemization. The hexad stereosequential analysis of photodegraded PLLA was investigated to specify the racemized positions within a chain in comparison with hydrolysis and thermal degradation. Results from (13)C NMR spectra of UV-irradiated PLLA samples indicated that the samples have racemized d-lactate units at chain ends. From the comparison of racemization behavior among photolysis, hydrolysis, and thermal degradation, it was confirmed that the preferential racemization behavior of each of these three degradation processes is characteristic and distinct, being identified as chain-end racemization, poor racemization, or internal-unit racemization, respectively. The characteristic chain-end racemization behavior of photolysis was first confirmed in this study.

Biomass-based composites from poly(lactic acid) and wood flour by vapor-phase assisted surface polymerization.

To prepare biomass-based composites in an environmentally benign manner, vapor-phase assisted surface polymerization (VASP) was applied to prepare the composites from wood flour and poly(l-lactic acid) (PLLA) without solvent. VASP of l,l-lactide successfully proceeded on the wood flour surfaces, resulting in surface coverage by newly generated PLLA. For obtained PLLA/wood flour composites, it was clarified that grafting of PLLA on wood flour surfaces had occurred to form covalently bonded composites, with the accumulated PLLA layers having crystallized in situ during VASP. Resulting PLLA layers showed very high crystallinity of 79.2% and a high melting point close to the equilibrium melting point. Moreover, thermal degradation behavior of the composites suggested a cooperative degradation manner of the components.

Chemical recycling of polyhydroxyalkanoates as a method towards sustainable development.

Chemical recycling of bio-based polymers polyhydroxyalkanoates (PHAs) by thermal degradation was investigated from the viewpoint of biorefinery. The thermal degradation resulted in successful transformation of PHAs into vinyl monomers using alkali earth compound (AEC) catalysts. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)s (PHBVs) were smoothly and selectively depolymerized into crotonic (CA) and 2-pentenoic (2-PA) acids at lower degradation temperatures in the presence of CaO and Mg(OH)(2) as catalysts. Obtained CA from 3-hydroxybutyrate sequences in PHBV was copolymerized with acrylic acid to produce useful water-soluble copolymers, poly(crotonic acid-co-acrylic acid) that have high glass-transition temperatures. The copolymerization of CA derived from PHA pyrolysis is an example of cascade utilization of PHAs, which meets the idea of sustainable development.

Polymorphic packing and dynamics of biodegradable poly(3-hydroxypropionate).

The packing and dynamics of the beta-, gamma-, and delta-forms of poly(3-hydroxypropionate) (P3HP), which represents the basic skeleton of bacterial poly(3-hydroxyalkanoate)s, were investigated by the variable-temperature FTIR and (13)C solid-state NMR measurements (SNMR). Under cooling, most of IR bands in the 1500-750 cm(-1) region were noted to be distinctively blueshifted and enhanced, which should reflect the increased intermolecular interaction and depend on the chain packing of each crystal form. Furthermore, the temperature-dependent splitting of vibration were found to occur at the CH2 bending and rocking for the gamma-form, and at the CH2 bending and C-O-C stretching for the delta-form, while be absent for the beta-form. All the FTIR results indicate that the gamma-form has a stronger intermolecular interaction than the beta-form, although both adopt the all-trans conformation. The IR evidence measured during heating further reveal that the melting of the tightly packed gamma-form would pass through some mesophase, which lacks the regular packing but hold the long-range order along the chains. The delta-form was also found to be tightly packed, and contain at least and most possibly two chains in one unit cell. The CP/MAS (13)C SNMR spectrum of the delta-form was compared with those of the beta- and gamma-forms, and was well explained by combining the gamma-gauche and gamma-eclipsed effects. With considering possible differences in the magnetic dipole-dipole interaction among three crystal forms, the molecular mobilities of crystalline phases were estimated by the values of (13)C spin-lattice relaxation time to rank as delta << gamma << beta. The diversified mobilities of three polymorphic crystalline phases, which is the key to crystalline-structure dependent biodegradability of P3HP, were discussed with considering the packing and conformation.

Crystalline-structure-dependent enzymatic degradation of polymorphic poly(3-hydroxypropionate).

The crystalline structure dependence of enzymatic degradation behavior was investigated for the polymorphic poly(3-hydroxypropionate) (P3HP), which has a basic backbone chemical structure of bacterial poly(3-hydroxyalkanoate)s (P3HAs). The P3HP films consisting of the beta-, gamma-, and/or delta-form crystal were cast or melt-crystallized as reported previously (Macromolecules 2005, 38, 6455; Macromolecules 2006, 39, 194-203) by controlling the molecular weight, crystallization temperature, and/or temperature of the melt. Their thermal properties, crystalline structures, morphologies, and (13)C solid spin-lattice relaxation dynamics were characterized by the differential scanning calorimetry, the wide-angle X-ray diffraction, the small-angle X-ray scattering (SAXS), and the (13)C solid-state NMR spectra (SNMR), respectively. Both the crystallinities and the lamellar thicknesses of P3HP films were found to decrease roughly in the order of beta-form > (or approximately) gamma-form > delta-form. From previous work, which indicates that the P3HA enzymatic degradation depends only on the degree of crystallinity and the lamellar thickness, their enzymatic degradation rates are then expected to increase in the order of beta-form < (or approximately) gamma-form < delta-form. Unexpectedly, their experimental P3HP enzymatic degradation rates in the presence of P3HA depolymerase isolated from Ralstonia pickettii T1 increase in the reverse order, i.e., delta-form < gamma-form < beta-form. The weight loss rate of the delta-form film is almost 1 order of magnitude smaller than that of the fastest degraded beta-form film. It is then strongly indicated that the crystalline structure plays a strikingly decisive role in the enzymatic degradation of P3HP. In particular, only when the conformation of crystalline chain accords with that of the bacterial poly(3-hydroxybutyrate) (P3HB) sample, i.e., the 2 1 helix conformation, is the P3HP sample degraded as slow as the P3HB sample. The inherent reason responsible for the unique P3HP enzymatic degradation behavior has been further clarified by comparing the molecular interaction and dynamics of polymorphic P3HP crystals.

Biosynthesis and biodegradability of copolythioesters from 3,3'-thiodipropionic acid and plant oils by Cupriviadus necator.

To prepare sulfur-containing natural polymers effectively, several plant oils and 3,3'-thiodipropionic acid (TDP) have been used as carbon sources for the biosynthesis of copolymer poly[(3-hydroxybutyrate)-co-(3-mercaptopropionate)] [poly(3HB-co-3MP)] by a wild-type bacterium Cupriviadus necator H16. By using the plant oils, copolymer accumulation and incorporation of 3MP units are greater than those of cases using sugars. The 3MP fraction is controllable over a range of 1-39 mol-% by adjusting the cultivation conditions. Microbial degradability of the copolymers has been examined in an activated sludge supernatant. The biodegradation proceeded by two mechanisms: surface erosion and auto-catalytic hydrolysis, depending on the 3MP unit fraction, and show preferential degradation of 3HB unit sequences.

Designed surface construction by photo-induced vapor-phase assisted surface polymerization of vinyl monomers using immobilized free radical initiators.

To build up finely designed patterns on solid surfaces, consecutive vapor-phase assisted surface photo-polymerization (VASP) of methyl methacrylate and styrene was carried out under UV-irradiation through a stripe-patterned photo-mask on Si-wafer and Au-plate surfaces, resulting in the reproduction of designed and multi-layered patterns made of block copolymer chains grafted from the surfaces.

Inclusion complex formation between alpha-cyclodextrin and biodegradable aliphatic polyesters.

Inclusion complexes (ICs) between alpha-cyclodextrin (alpha-CD) and three kinds of biodegradable aliphatic polyesters with different sequence lengths of the monomeric repeating units poly(3-hydroxypropionate) [P(3HP)], poly(4-hydroxybutyrate) [P(4HB)] and poly(epsilon-caprolactone)(PCL) were prepared by mixing a solution of alpha-CD with that of the polymer, followed by stirring. The ICs were obtained as insoluble precipitates and characterized by FT-IR, WAXD and DSC. All measurements showed that the polymer chains of all three kinds of polyester were included into the alpha-CD cavity and formed ICs with different stoichiometries. WAXD patterns and thermal analysis indicated that these ICs possessed a channel structure and the crystallization of the polyester chains was suppressed upon inclusion into the alpha-CD cavity.