Thermal degradation and cyclodepolymerization of poly(ethylene terephthalate-co-isophthalate)s

The thermal degradation of poly(ethylene terephthalate-co-isophthalate)s (PETIs) is investigated by using isothermal thermogravimetric analysis at the temperature range of 280–310°C. The degradation rate of PETIs is increased as the mole ratio of ethylene isophthaloyl (EI) units in PETIs increases. The activation energies for the thermal degradation of poly(ethylene terephthalate), PETI(5/5), and poly(ethylene isophthalate) are 33.4, 16.6, and 8.9 kcal/mole, respectively. The degradation rate of PETIs is influenced by their volatile cyclic oligomer components formed during the polymerization and the thermal degradation. It is simulated by the rotational isomeric state model that the content of cyclic dimer in PETIs, which is the most volatile cyclic oligomer component, increases with the EI units in PETIs.     

Kinetics of two-step emulsion polymerization of poly(n-butyl methacrylate)/poly(methyl methacrylate) polymer networks

Poly(n-butyl methacrylate)/poly(methyl methacrylate) polymer networks were synthesized by two-step emulsion polymerization with sodium dodecylsulfonate and polyoxyethylene nonylphenolether as the emulsifier, distilled water as the continuous medium, and potassium persulfate as the initiator. The kinetics of two-step emulsion polymerization was studied. Effects of emulsifier concentration, initiator concentration, and polymerization temperature on monomer conversion and polymerization rate were investigated in detail. Experimental data indicate that both the steady state polymerization rate and monomer conversion increase with the augment of emulsifier concentration, initiator concentration, or reaction temperature.     

Miscibility and crystallization behaviors of poly(trimethylene terephthalate)/poly(ethylene naphthalate) blends

Poly(trimethylene terephthalate) (PTT)/poly(ethylene naphthalate) (PEN) blends of various compositions were prepared by the solution-blending and melt-blending methods. The changes in miscibility and crystallization behaviors of the blends upon thermal treatment above the melting temperature of the blends at 280°C were investigated by using DSC, DMA,¹H NMR, and SAXS analyses. Without any thermal treatment, the blend systems were not miscible, and the thermal transitions, such as glass transition, cold crystallization, and crystal melting of the individual components were observed in the DSC and DMA analyses. With thermal treatment, though, they became miscible as the thermal transitions of each component disappeared and single glass transition peaks were observed in the thermal analysis. The chain randomness determined using¹H NMR spectroscopy revealed that thermal treatment at 280°C for more than 30 min brought about transesterification reactions between the PTT and PEN segments resulting in an increase in their miscibility. These results were confirmed by the small angle X-ray analysis conducted to determine the long period (L), the thickness of the crystalline lamella stack (l _c ), and the thickness of the amorphous region (l _a ). After short thermal treatment, the melt-blended sample followed the values for the individual components. However, with extended thermal treatment, the blend became homogeneous, possessing different crystalline morphologies which resulted in different values ofL, l _c , andl _a .     

Thermal decomposition kinetics of copolymers derived from<Emphasis Type="Italic">p</Emphasis>-dioxanone,L-lactide and poly(ethylene glycol)

The kinetic parameters, including the activation energyE, the reaction ordern, and the pre-exponential factorZ, of the degradation of the copolymers based on the poly(L-lactide) (PLLA) or poly(p-dioxanone-co-L-lactide) (PDO/PLLA) and diol-terminated poly(ethylene glycol) (PEG) segments have been evaluated by the single heating methods of Friedman and Freeman-Carroll. The experimental results showed that copolymers exhibited two degradation steps under nitrogen that can be ascribed to PLLA or PDO/PLLA and PEG segments, respectively. However, copolymers exhibited almost single degradation step in air. Although the values of initial decomposition temperature were scattered, copolymers showed the lower maximum weight loss rate and degradation-activation energy in air than in nitrogen whereas the higher value of temperature at the maximum rate of weight loss was observed in air.     

Synthesis and hydrophilicity of poly(trimethylene 2,6-naphthalate)/poly(ethylene glycol) copolymers

Poly(trimethylene 2,6-naphthalate) (PTN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two-step melt copolymerization process of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) with 1,3-propanediol (PD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structure, thermal property, and hydrophilicity of these copolymers were studied by proton nuclear magnetic resonance (¹H-NMR) analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and by contact angle, moisture content, and instantaneous elastic recovery measurements. The intrinsic viscosity and the instantaneous elastic recovery of the PTN/PEG copolymers increased with increasing PEG molecular weight and content, whereas the glass transition, melting, and cold crystallization temperatures, and the heat of fusion of the PTN/PEG copolymers all decreased with increasing PEG molecular weight or content. The thermal stability of the copolymers was not affected by PEG molecular weight or content. The hydrophilicity, as determined by contact angle and moisture content measurements of the copolymer films, was significantly improved with increasing PEG molecular weight and content.     

Compatibilization of immiscible poly(<Emphasis Type="Italic">l</Emphasis>-lactide) and low density polyethylene blends

Blends of poly(l-lactide) (PLA) and low density polyethylene (LDPE) were prepared by melt mixing in order to improve the brittleness of PLA. A reactive compatibilizer with glycidyl methacrylate (GMA), PE-GMA, was required as a compatibilizer due to the immiscibility between PLA and LDPE. It contributes to reduce the domain size of dispersed phase and enhance the tensile properties of PLA/LDPE blends, especially for PLA matrix blends. A reaction product between PLA and PE-GMA, which was formed during melt-mixing and considered to act as a reactive compatibilizer, was characterized using¹H-NMR spectroscopy.     

Surface modification of poly(lactic acid) by UV/Ozone irradiation

Hydrophobic poly(lactic acid), PLA, was modified to give hydrophilicity and dyeability to cationic dyes via UV/O₃ irradiation. The UV irradiation treatment caused ester linkage of PLA surface to break down resulting in reduced molecular weight and generation of new photooxidized products as indicated in subtracted ATR spectra and ESCA analysis. It was found that water contact angle decreased from 61 ° to 39 ° and surface energy slightly increased with increasing UV energy, which was attributed to significant contribution of polar component rather than nonpolar component resulting from the surface photooxidation of PLA. Also the surface treatment increased dyeability of PLA to C.I. Basic Blue 41 in terms of both K/S and %E. The increased dyeability may be due to photochemically introduced anionic and dipolar dyeing sites which electrostatically interact with the cationic dye as ascertained by the decreased zeta potential and its pH dependence of the modified PLA.     

Properties of thermoplastic starch from cassava bagasse and cassava starch and their blends with poly (lactic acid)

Cassava bagasse is an inexpensive and broadly available waste byproduct from cassava starch production. It contains roughly 50% cassava starch along with mostly fiber and could be a valuable feedstock for various bioproducts. Cassava bagasse and cassava starch were used in this study to make fiber-reinforced thermoplastic starch (TPS_B and TPS_I, respectively). In addition, blends of poly (lactic acid) and TPS_I (20%) and TPS_B (5, 10, 15, 20%) were prepared as a means of producing low cost composite materials with good performance. The TPS and PLA blends were prepared by extrusion and their morphological, mechanical, spectral, and thermal properties were evaluated. The results showed the feasibility of obtaining thermoplastic starches from cassava bagasse. The presence of fiber in the bagasse acted as reinforcement in the TPS matrix and increased the maximum tensile strength (0.60 MPa) and the tensile modulus (41.6 MPa) compared to cassava starch TPS (0.40 and 2.04 MPa, respectively). As expected, blending TPS with PLA reduced the tensile strength (55.4 MPa) and modulus (2.4 GPa) of neat PLA. At higher TPS_B content (20%) the maximum strength (19.9 MPa) and tensile modulus (1.7 GPa) were reduced about 64% and 32%, respectively, compared to the PLA matrix. In comparison, the tensile strength (16.7) and modulus (1.2 GPa) of PLA blends made with TPS_I were reduced 70% and 51% respectively. The fiber from the cassava bagasse was considered a filler since no increase in tensile strength of PLA/TPS blends was observed. The TPS_I (33.1%) had higher elongation to break compared to both TPS_B (4.9%) and PLA (2.6%). The elongation to break increased from 2.6% to 14.5% by blending TPS_I with PLA. In contrast, elongation to break decreased slightly by blending TPS_B with PLA. Thermal analysis indicated there was some low level of interaction between PLA and TPS. In PLA/TPS_B blends, the TPS_B increased the crystallinity of the PLA component compared to neat PLA. The fiber component of TPS_B appeared to have a nucleating effect favoring PLA crystallization.     

Formation of metal complex in a poly(hydroxamic acid) resin bead

Poly(hydroxamic acid) resin beads were prepared and complexed with various metal ions. We used IR spectroscopy to investigate the structure of metal complex. It proved that the products formed by introduction of metal ions gave stable and colored complex. It was found that the resin bead as synthesized would be a good column packing material for continuous extraction. Energy dispersive spectroscopy was used to study the distribution of metal ions in the resin matrix. It could be tentatively concluded that adsorption and diffusion of metal ions in the chelating resins mainly depended on the loading of the resin matrix which indicated interacting sites with metal ions.     

Crystallization of poly(vinylidene fluoride)-SiO2 hybrid composites prepared by a Sol-gel process

Organic-inorganic hybrid composites consisting of poly(vinylidene fluoride) (PVDF) and SiO₂ were prepared through a sol-gel process and the crystallization behavior of PVDF in the presence of SiO₂ networks was investigated by spectroscopic, thermal and x-ray diffraction measurements. The hybrid composites obtained were relatively transparent, and brittleness increased with increasing content of tetraethoxysilane (TEOS). It was regarded from FT-IR and DSC thermal analyses that at least a certain interaction existed between PVDF molecules and the SiO₂ networks. X-ray diffraction measurements showed that all of the hybrid samples had a crystal structure of PVDFγ-phase. Fresh gel prepared from the sol-gel reaction showed a very weak x-ray diffraction peak near 2θ=21° due to PVDF crystallization, and intensity increased gradually with time after gelation. The crystallization behavior of PVDF was strongly affected by the amount of SiO₂ networks. That is, SiO₂ content directly influenced preference and disturbance for crystallization. In polymer-rich hybrids, SiO₂ networks had a favorable effect on the extent of PVDF crystallization. In particular, the maximum percent crystallinity of PVDF occurred at the content of 3.7 wt% SiO₂ and was higher than that of pure PVDF. However, beyond about 10 wt% SiO₂, the crystallization of PVDF was strongly confined.     

Effects of lipase on poly(lactic acid) fibers

Two types of lipases, L3126 and Lipex 100L, were used to modify the surface of poly(lactic acid) (PLA) fiber by measuring weight loss percentage and wettability of the fiber in this work. The influence factors were discussed and optimized based on single-factor experiments. The optimal conditions for the modification of poly(lactic acid) fiber with lipases were determined as follows: incubation with lipase L3126 of 0.5 g/l at 45 °C and pH 8.5 for 8 hours and incubation with lipase of 10 ml/l at 40 °C and pH 7.5 for 10 hours. Lipase L3126 showed higher biodegradation ability to poly(lactic acid) fiber than lipase Lipex 100L. The scanning electron microscopy confirmed that both of the two lipases could lead to the formation of etching characters on treated poly(lactic acid) fibers in comparison with the blank samples. Furthermore, the wettability of the fibers treated with the lipases was evidently improved, especially Lipase L3126.     

X-ray diffraction studies of poly(aryl ether ether ketone) fibers with different degrees of crystallinity and orientation

A selection of commercially available poly(ethylene terephthalate) fibers with different degrees of molecular alignment and crystallinity have been investigated utilizing a wide range of techniques including optical microscopy, infrared spectroscopy together with thermal and wide-angle X-ray diffraction techniques. Annealing experiments showed increased molecular alignment and crystallinity as shown by the increased values of birefringence and melting enthalpies. Crystallinity values determined from thermal analysis, density, unpolarized infrared spectroscopy and X-ray diffraction are compared and discussed in terms of the inherent capabilities and limitations of each measurement technique. The birefringence and refractive index values obtained from optical microscopy are found to decrease with increasing wavelength of light used in the experiments. The wide-angle X-ray diffraction analysis shows that the samples with relatively low orientation possess oriented non-crystalline array of chains whereas those with high molecular orientation possess well defined and oriented crystalline array of chains along the fiber axis direction. X-ray analysis showed increasing crystallite size trend with increasing molecular orientation. SEM images showed micro-cracks on low oriented fiber surfaces becoming smooth on highly oriented fiber surfaces. Excellent bending characteristics were observed with knotted fibers implying relatively easy fabric formation.     

Evaluation of cotton byproducts as fillers for poly(lactic acid) and low density polyethylene

Polymeric composites based on cotton burr and cottonseed bull have been prepared by melt blending and extrusion. For poly(lactic acid) (PLA) and low-density polyethylene (LDPE), addition of the fillers slightly changed the composite's thermal properties but significantly decreased the composite's mechanical properties. Heat treatment prior to extrusion resulted in composites with better tensile strength and Young's modulus. The use of maleic anhydride and peroxide only slightly improved the physical properties of the LDPE materials, but the effect was less clear for the PLA materials. The PLA-filler composites may be useful for lowering the cost of the materials in applications that can tolerate the decreased properties. In addition, the addition of fillers to LDPE might be beneficial in applications to improve stiffness or to improve biodegradability.     

Soy protein isolate/poly(lactic acid) injection-molded biodegradable blends for slow release of fertilizers

A slow release fertilizer system consisting of materials derived exclusively from biomass, and suitable for i) production of injection-molded parts such as containers for growing plants, and ii) use as granules, is reported. Soy (Glycine max L. Merr.) protein isolate/poly(lactic acid) blends plasticized with triacetin (SPI/PLA-TA) were used as matrix for NPK fertilizer incorporation. Upon melt processing, this composite material formed a highly ordered porous matrix of SPI in which PLA domains are homogeneously dispersed with NPK salts. Dynamic conductivity measurements indicated good release properties as the cumulative amount increased much slower with time as compared to pure NPK sample. Biodegradation was accessed by examining weight loss and surface morphology as a function of incubation time in soil.     

Oil content and fatty acid composition of promising IndianBrassica campestris L. (Toria) genotypes

Seeds of sixty four genotypes ofBrassica campestris L. (Toria) were analyzed for oil content and fatty acid composition. Oil content varied from 38.9% to 44.6%. Major fatty acids viz. oleic, linoleic, linolenic, eicosenoic and erucic acids exhibited ranges from 10.1% to 17.3%, 5.9% to 14.5%, 5.2% to 15.0%, 7.7% to 13.7% and 39.6% to 59.9%, respectively. Compared to the standard cultivar ITSA, four genotypes contained 5 to 8% lower content of erucic acid; and six genotypes contained significantly higher content of linoleic acid. Oil was positively correlated with erucic acid. The observed inverse relationship between linoleic and erucic acid contents might be utilized in breeding nutritionally better Toria cultivars with both high linoleic and low erucic acid contents.     

Preparation and characterization of nanoscaled poly(vinyl alcohol) fibers via electrospinning

Nanoscaled PVA fibers were prepared by electrospinning. This paper described the electrospinning process, the processing conditions, fiber morphology, and some potential applications of the PVA nano-fibers. PVA fibers with various diameters (50–250 nm) were obtained by changing solution concentration, voltage and tip to collector distance (TCD). The major factor was the concentration of PVA solution which affected the fiber diameter evidently. Increasing the concentration, the fiber diameter was increased, and the amount of beads was reduced even to 0%. The fibers were found be efficiently crosslinked by glyoxal during the curing process. Phosphoric acid was used as a catalyst activator to reduce strength losses during crosslinking. Scanning electron micrograph (SEM) and differential scanning calorimetric (DSC) techniques were employed to characterize the morphology and crosslinking of PVA fibers. It was found that the primary factor which affected the crosslinking density was the content of chemical crosslinking agent.     

Spinodal phase separation and isothermal crystallization behavior in blends of VDF/TrFE(75/25) copolymer and poly(1,4-butylene adipate) (I)

Phase behavior and spinodal phase separation kinetics in binary blends of a random copolymer of vinylidene fluoride and trifluoroethylene (75/25) [P(VDF/TrFE)] and poly(1,4-butylene adipate) (PBA) have been investigated by means of optical microscopic observation and time-resolved light scattering. The blends exhibited a typical lower critical solution temperature (LCST)∼34 °C above the melting temperature of the P(VDF/TrFE) crystals over the entire blend composition range. P(VDF/TrFE) and PBA were totally miscible in the temperature gap between the melting point of P(VDF/TrFE) and the LCST. Temperature jump experiments of the 3/7 P(VDF/TrFE)/PBA blend were carried out on a light-scattering apparatus from a single-phase melt state (180 °C) to a two-phase region (205∼215 °C). Since the late stage of spinodal decomposition (SD) is prevalent in the 3/7 blend, SD was analyzed using a power law scheme. Self-similarity was preserved well in the late stage of SD in the 3/7 blend.     

Synthesis,structure, and thermal property of poly(trimethylene terephthalate-<Emphasis Type="Italic">co</Emphasis>-trimethylene 2,6-naphthalate) copolymers

Poly(trimethylene terephthalate-co-trimethylene 2,6-naphthalate)s (P(TT-co-TN)s) with various copolymer composition were synthesized, and their chain structure, thermal property and crystalline structure were investigated by using¹H-NMR spectroscopy, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD), respectively. It was found from sequence analysis that all the P(TT-co-TN) copolymers synthesized have a statistical random distribution of TT and TN units. It was also observed from DSC thermograms that the glass transition temperature increases linearly with increasing the TN comonomer content, whereas the melting temperature of copolymer decreases with increasing the corresponding comonomer content in respective PTT- and PTN-based copolymer, showing pseudo-eutectic melting behavior. All the samples melt-crystallized isothermally except for P(TT-co-66 mol % TN) exhibit multiple melting endotherms and clear X-ray diffraction patterns. The multiple melting behavior originates from the dual lamellar population and/or the melting-recrystallization-remelting. The X-ray diffraction patterns are largely divided into two classes depending on the copolymer composition, i.e., PTT and PTNβ-form diffraction patterns, without exhibiting cocrystallization.     

Degradation behaviour of poly(lactic acid) films and fibres in soil under Mediterranean field conditions and laboratory simulations testing

Long-term degradation/disintegration behaviour, indicative of the biodegradation in soil behaviour of poly(lactic acid) films and fibres, was studied in natural Mediterranean soil environment during an eleven-month trial in the experimental field. In parallel, simulated soil burial experiments were carried out under controlled laboratory conditions. The degradation/disintegration behaviour of PLA was analysed using visual inspection, mechanical testing, DSC and FTIR analysis. The influence of the thickness and the type of the materials (film vs. fibre) on disintegration was investigated under the given mild conditions. For comparison purposes, degradation/disintegration of PLA film was also studied under low temperature composting conditions (house composting). During long-term exposure under natural soil environment dominated by complex and uncontrolled biotic-abiotic conditions and Mediterranean climatic conditions and under house composting conditions, PLA film samples of different thicknesses were partially, to a rather low degree, degraded mechanically or slightly disintegrated. The results showed that degradation behaviour of bio-based polymers like poly(lactic acid) in a real soil environment is a complex phenomenon, following different patterns regarding morphological changes.     

Copper metallization of poly(ethylene terephthalate) fabrics via intermediate polyaniline layers

Poly(ethylene terephthalate) fabrics were metallized through electroless plating of copper. The copper plating was performed on palladium-decorated polyaniline surfaces, and polyaniline was present as an intermediate layer on fabrics to facilitate palladium formation. Different oxidation states of polyaniline were tested in their efficacy in Pd (II) reduction and subsequent Cu plating. X-ray photoelectron spectroscopy was used to monitor the surface changes along the metallization procedure, and surface resistance was measure to probe the electrical properties of the metallized fabrics.