Improving the Processing Ability and Mechanical Strength of Starch/Poly(vinyl alcohol) Blends through Plasma and Acid Modification

Summary: In this study, maleic anhydride (MA), and citric acid (CA) used as the processing additive and plasma treatment to improve the processing ability and mechanical strength of biodegradable starch/poly (vinyl alcohol) (PVA) blends were studied. The melt flow index (MFI) of starch/ glycerol/PVA (300g/60g/80g) blend was increased from 2.3g/10min to 32.7g/10min by adding 3g of MA and to 130 g/10min by adding MA and plasma treatment. The tensile strength of starch/glycerol/PVA blend increased from 3.48 to 6.21 MPa by adding 1.5g of MA and 1.5g of CA, while it increased to 6.26 MPa by plasma treatment. Esterification reaction which was evidenced by FTIR has been showed to improve the compatibility between starch and PVA when MA was dissolved into glycerol and glycerol grafted onto plasma pretreatment PVA. Thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) imaging were used to study the morphology of extruded blends.     

高相容性TDI-三聚体的合成及其热稳定性

高相容性TDI-三聚体的合成及其热稳定性;甲苯二异氰酸酯三聚体; 相容性; 热重分析     

Thermal Degradation Behavior and Kinetic Analysis of Biodegradable Polymers Using Various Comparative Models, 1

Thermal degradation behavior of a biodegradable polymer (PBS) has been investigated by conventional and MTGA methods. The kinetic parameters of degradation were calculated by a general analytical solution and by the Coats‐Redfern, Ozawa, Horowitz‐Metzger, and MTGA methods. The results reveal that the reaction mechanism at lower temperature is probably the F1 model through the reaction of random chain cleavage via cis‐elimination. However, the reaction mechanism at higher temperature is likely to be D1 model because of the dominant diffusion control effect.

     

Gamma Irradiation Effects on Mechanical and Thermal Properties and Biodegradation of Poly(3-hydroxybutyrate) Based Films

Summary: Their biodegradable properties make polyhydroxyalkanoates (PHAs) ideal candidates for innovative applications. Many studies have been primarily oriented to poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-valerate) (PHBV) and afterwards to blends of PHAs with synthetic biodegradable polymers, such as poly(ε-caprolactone) (PCL). Medical and pharmaceutical devices require sterilization and γ irradiation could provide a proper alternative since it assures storage stability and microbiological safety. This contribution presents the effect of γ irradiation on the mechanical and thermal properties and on the biodegradation of PHB, PHBV and a commercial PHB/PCL blend. Samples, prepared by compression moulding, were irradiated in air at a constant dose rate of 10 kGy/h, from 10 to 179 kGy. Polymer chain scission was assessed by changes in the molecular weight, thermal properties and tensile behaviour. The correlation between absorbed dose and changes in the mechanical properties and biodegradation is discussed in detail. The optimum dose to guarantee microbiological sterilization without damage of the structure or meaningful loss of the mechanical properties is also reported.     

Thermal Stability and Flammability of Polypropylene-Silsesquioxane Nanocomposites

This article presents a study of the thermal stability of polypropylene-based nanocomposites filled with tetrasilanolphenyl silsesquioxane (phPOSS). Nanofillers were introduced into a polypropylene matrix in three different amounts: 2, 5, and 10 wt.%. Investigations were carried out by means of thermogravimetric analyses conducted in inert and oxidizing atmospheres, Fourier transform-infrared spectroscopy, scanning electron microscopy, and flammability UL-94 test. The addition of phPOSS into the polymeric matrix increased thermal stability in comparison to neat iPP and introduced significant changes in the flammability of iPP/phPOSS nanocomposites.     

Kinetics of the Thermal and Thermo‐Oxidative Degradation of a Polystyrene–Clay Nanocomposite

Summary: Thermogravimetry and differential scanning calorimetry have been used to study the thermal and thermo‐oxidative degradation of polystyrene (PS) and a PS–clay nanocomposite. An advanced isoconversional method has been applied for kinetic analysis. Introduction of the clay phase increases the activation energy and affects the total heat of degradation, which suggests a change in the reaction mechanism. The obtained kinetic data permit a comparative assessment of the fire resistance of the studied materials.

The change in activation energy for the degradation of PS and the PS–clay nanocomposite with the extent of polymer conversion.     

Melting Processing of Biodegradable Cellulose Diacetate/Starch Composites

Natural polymers and their derivatives are attracting increasing interest as promising biodegradable materials that can meet the environmental and recycling demands from society. This study prepared biodegradable composites of cellulose diacetate and starch, and examined their physical and thermal properties. In addition, the morphology of the composites was examined by scanning electron microscopy. For melt processing, epoxidized soybean oil, as a lubricant, and triacetine, as a plasticizer, were added to the composites. The optimal conditions for the preparation of the biodegradable composites were determined. Increasing the amount of starch in the composites resulted in further enhancement of the processability of cellulose diacetate. The tensile strength and Young's modulus decreased, and the amount of elongation and T_g value increased with increasing amount of starch.     

Nylon Based Nanocomposites: Influence of Calcium Carbonate Nanoparticles on the Thermal Stability

In this paper thermal and thermo-oxidative stability of nylon 6 based nanocomposites containing up to 5% by weight of fatty acid coated calcium carbonate (CaCO₃) nanoparticles is studied. Thermal stability of compression-moulded samples was evaluated by thermogravimetric analysis (TG) under air and nitrogen atmosphere. Kinetic analysis of TG data was performed by using the Flynn-Wall-Ozawa method. Results show that the presence of coated nanoparticles adversely affects the thermal and thermo-oxidative stability of nylon 6. Kinetic analysis shows that a complex, multi-step decomposition process occurs. Moreover, the presence of nanoparticles do not affect the rate limiting step of nylon 6 decomposition in air, while under nitrogen atmosphere the decomposition process occurs through a diffusion-driven regime in presence of high amounts of CaCO₃.     

The Study of Kinetics of Poly[(R,S)-3-hydroxybutyrate) Degradation Induced by Carboxylate

Summary: The carboxylate induced degradation of the poly[(R,S)-3-hydroxybutyrate] (PHB) has been investigated with non-isothermal measurements. The apparent activation energies for PHB degradation have been determined. Application of the Kissinger's and Flynn-Wall-Ozawa's method for TG and DSC derived data gave good correlation of the results proving applicability of the non-isothermal DSC measurements for the study. Moreover, dependence of the apparent activation energies on the activity of the carboxylate has been found.     

淀粉与丙烯酸甲酯的接枝共聚物作为生物降解塑料的研究

如何解决废弃塑料制品的再资源化和使用无污染的降解塑料是当今人类急待解决的热点课题．淀粉与丙烯酸甲酯（MA）进行接技共聚以制备塑料发泡产品的研究已有报道［‘－‘1，一般认为塑料中淀粉含量在40％以上的产品，很容易在土壤中被微生物降解掉［‘］．这些研究都是在水溶液体系中进行的，本文的目的在于开发高淀粉含量的接校共聚物，为此对比了在3种不同体系（MA－CH3OHA12O三元均相溶液体系，水溶液体系和乳液体系）中得到的接校共聚物的力学性能、形态观察与组成情况，发现单纯追求高接技效率与接枝链MA的高分子量并不一定能得到…     

单壁纳米碳管的纯化研究

A purification method to remove the metal catalysts and impurity carbon materials from arc-discharge-grown single-walled carbon nanotubes (SWCNTs) has been developed. Microporous membrane and the oxidation in the air for the crude SWCNTs were used to eliminate the coexisting metal catalysts nanoparticles，carbon nanoparticles and amorphous carbon. Then we used the high resolution transmission electron microscopy (HRTEM) to characterize the crude SWCNTs prepared by arc-discharge method and the purified SWCNTs. The Raman spectra and the thermogravimetric analysis (TGA) were also utilized to analyze the approach of our purification for SWCNTs. With this method the SWCNTs with the purity more than 95% could be obtained.     

Partially pyrolyzed poly(dimethylsiloxane)‐based networks: Thermal characterization and evaluation of the gas permeability

In this investigation, the preparation and characterization of partially pyrolyzed membranes based on poly(dimethylsiloxane) (PDMS) are described. These membranes were obtained by the crosslinking of silanol‐terminated PDMS with multifunctional nanoclusters derived from the reaction of pentaerythritoltriacrylate with 2‐aminoethyl‐3‐aminopropyltrimethoxysilane and the in situ polycondensation of tetraethylortosilicate, followed by the thermal treatment of the resulting membranes at different temperatures. The partially pyrolyzed membranes were characterized with infrared spectroscopy, thermogravimetry, elemental analyses, dynamic mechanical analysis, small‐angle X‐ray scattering, and scanning electron microscopy. The membranes exhibited improvements in the thermal stability and mechanical strength. Even with distinct compositions with respect to the Si/O and Si/C ratios, the flexibility of these materials was maintained. The flux rates of the gases through the membranes were measured for N₂, H₂, O₂, CH₄, and CO₂, at 25 °C. The permeability of the membranes changed with increases in the pyrolysis and oxidation temperatures. These membranes could be described as PDMS chains separated by inorganic clusters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 299–309, 2007.     

Thermal stability of reversible addition–fragmentation chain transfer/macromolecular architecture design by interchange of xanthates chain‐transfer agents

A series of chain‐transfer agents used in reversible addition–fragmentation chain transfer/macromolecular architecture design by interchange of xanthates polymerizations were subjected to thermogravimetric analysis and gas chromatography/mass spectrometry to assess their stability to heat and to determine their degradation pathways. The effects of the chain‐transfer‐agent class and structure on the thermal stability are described. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6980–6987, 2006     

Isolation and Determination of Beta-Carotene in Carrots by Magnetic Chitosan Beta-Cyclodextrin Extraction and High-Performance Liquid Chromatography (HPLC)

Beta-carotene is a carotenoid with strong antioxidant activity that has been used in many areas and attracted significant attention. Among the articles reported, however, there are few examples of the convenient and eco-friendly use of magnetic chitosan biopolymers to extract beta-carotene. This paper reports the ultrasonic-assisted solid phase extraction of beta-carotene. The beta-carotene in carrot samples was extracted using synthesized magnetic chitosan beta-cyclodextrin biopolymers prior to high-performance liquid chromatography (HPLC) detection. Under the optimal conditions, the beta-carotene content of carrot was found to be 41.06?±?0.02?μg/g. This newly developed method using magnetic chitosan cyclodextrin biopolymers is a promising method for the ultrasonic-assisted solid phase extraction of carotenoids from vegetables because the procedure is facile and rapid and the magnetic biopolymers can be removed using simple process.     

Effect of Hydration on Silk Film Material Properties

Effects of hydration on silk fibroin film properties were investigated for water‐annealed and MeOH‐treated samples. Hydration increased thickness by 60% for MeOH‐immersed films, while water‐annealed samples remained constant. MeOH‐immersed films showed an 80% mass loss due to water, while water‐annealed lost only 40%. O₂ permeability was higher in MeOH‐immersed films with Dk values of 10^?10 (mL O₂ · cm) · (cm^?1 · s^?1 · mmHg^?1), while those of water‐annealed films reached only one fifth of this value. All films showed a decrease in Young's modulus and increased plastic deformation by two orders of magnitude when submerged in saline solution. FT‐IR showed that β‐sheet content in water‐annealed films increased with increasing water vapor pressure, while MeOH‐immersed films showed no change.

     

Development and Characterization of Novel Composite Films Based on Soy Protein Isolate and Oilseed Flours

The possibility of using oilseed flours as a waste source for film-forming materials with a combination of soy protein isolate in preparation of edible films was evaluated. Physical, mechanical and barrier properties were determined as a function of the oilseed type: hemp, evening primrose, flax, pumpkin, sesame and sunflower. It was observed that the addition of oilseed flours increased the refraction and thus the opacity of the obtained films from 1.27 to 9.57 A mm⁻¹. Depending on the type of flours used, the edible films took on various colors. Lightness (L*) was lowest for the evening primrose film (L* = 34.91) and highest for the soy protein film (L* = 91.84). Parameter a* was lowest for the sunflower film (a* = −5.13) and highest for the flax film (a* = 13.62). Edible films made of pumpkin seed flour had the highest value of the b* color parameter (b* = 34.40), while films made of evening primrose flour had the lowest value (b* = 1.35). All analyzed films had relatively low mechanical resistance, with tensile strength from 0.60 to 3.09 MPa. Films made of flour containing the highest amount of protein, pumpkin and sesame, had the highest water vapor permeability, 2.41 and 2.70 × 10⁻⁹ g·m⁻¹ s⁻¹ Pa⁻¹, respectively. All the edible films obtained had high water swelling values from 131.10 to 362.16%, and the microstructure of the films changed after adding the flour, from homogeneous and smooth to rough. All blended soy protein isolate–oilseed flour films showed lower thermal stability which was better observed at the first and second stages of thermogravimetric analysis when degradation occurred at lower temperatures. The oilseed flours blended with soy protein isolate show the possibility of using them in the development of biodegradable films which can find practical application in the food industry.     

Photo Polymerized Interpenetrating Polymer Network of Poly(antimony acrylate) and Poly(arsenic acrylate): Synthesis and Characterization

A series of IPN based on poly(antimony acrylate) and poly(arsenic acrylate) have been synthesized by a sequential mode of synthesis. Formation of complex based on “polymer solvent” method reflects the contraction of the polymer coils by determining the value of mutual interaction constant (k_AB) in different solvents such as dimethylsulphoxide (DMSO) (k_AB=0.60); dimethylformamide (DMF) (k_AB=0.42); dioxane (k_AB=0.26) predicting weak Vander Waal interaction. The scanning electron microscopy reveals dual phase morphology of both metal acrylates. The infrared spectrum indicates characteristic frequencies of (>C?O) at 1730 cm^?1,thus giving structural evidence for IPN. The properties namely percentage swelling, average molecular weight between crosslinks(M_c),Young's modulus, increases with concentrations of linear polymer(polyantimony acrylate) and initiator (benzoyl peroxide). However, it decreases with concentrations of monomer (arsenic acrylate) and crosslinker (divinyl benzene).The value of activation energy calculated from thermo gravimetric analysis is 15 KJ/mol.     

Biodegradable poly(alkylene succinate) blends: Thermal behavior and miscibility study

New binary blends composed of poly(ethylene succinate) and poly(propylene succinate) or poly(ethylene succinate) and poly(butylene succinate) were prepared. Both PESu/PPSu and PESu/PBSu systems belong to semicrystalline/semicrystalline pairs. The miscibility and crystallization behavior was investigated using differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), and polarizing light microscopy (PLM). Blends of PESu and PPSu exhibited a single composition dependent glass transition temperature over the entire range of composition, indicating that the system is miscible. The melting point depression of the high melting temperature component, PESu, was analyzed according to the Nishi‐Wang equation. A negative polymer–polymer interaction parameter was obtained, indicating that the blends are thermodynamically miscible in the melt. The two components crystallized sequentially when the blends were cooled rapidly to a low temperature. DSC traces of PESu/PBSu blends after quenching showed two distinct composition dependent glass transition temperatures between those of the neat polymers, showing that the polymers are partially miscible. The amorphous PESu/PBSu blends in the intermediate compositions showed three cold‐crystallization peaks, indicating the influence of mixing. The crystallization rates of PBSu were reduced and those of PESu were increased. WAXD showed reduced crystallinity and peak broadening in the patterns of the blends of intermediate compositions, while no spherulites could be detected by PLM. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 584–597, 2006