Biodegradable polymer blends of poly(3-hydroxybutyrate) and starch acetate

The thermal behaviour and phase morphology of poly(3-hydroxybutyrate) (PHB) and starch acetate (SA) blends have been studied by differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy and polarizing optical microscopy. PHB/SA blends were immiscible. The melting temperatures of PHB in the blends showed some shift with increase of SA content. The melting enthalpy of the PHB phase in the blend was close to the value for pure PHB. The glass transition temperatures of PHB in the blends remained constant at 9°C. The FTIR absorptions of hydroxyl groups of SA and carbonyl groups of PHB in the blends were found to be independent of the second component at 3470cm^-1 and 1724cm^-1, respectively. The crystallization of PHB was affected by the addition of the SA component both from the melt on cooling and from the glassy state on heating. The temperature and enthalpy of non-isothermal crystallization of PHB in the blends were much lower than those of pure PHB. The crystalline morphology of PHB crystallized from the melt under isothermal conditions varied with SA content. The cold crystallization peaks of PHB in the blends shifted to higher temperatures compared with that of pure PHB. ©1997 SCI     

Thermodynamic hydrogen bonding inpoly(styrene‐co‐acrylic acid)/poly(styrene‐co‐4‐N,N‐dimethylacrylamide) blends

FTIR study of the hydrogen bonding interactions within blends of different ratios of poly(styrene‐co‐acrylic acid) containing 18, 27, and 32 mol% of acrylic acid (SAA) and poly(styrene‐co‐N,N‐dimethylacrylamide) containing 17 mol% of N,N‐dimethylacrylamide (SAD‐17) was carried out qualitatively and quantitatively in the temperature range varying from room temperature to 210°C. Two new bands characterizing these interactions appeared in the 1800–1550 cm^–1 region at 1730 cm^–1 and 1616 cm^–1 and are attributed to “liberated” carbonyl group of the acidic copolymer and the “associated amide” carbonyl group, respectively. Equilibrium constants describing both the self‐association K₂ and inter‐association K_A and the enthalpy of hydrogen bonding formation in the different blends were experimentally determined using a curve fitting analysis of the infra‐red spectra as a function of temperature using the appropriate equations derived from the Painter‐Coleman association model. The obtained results confirm the miscibility of these blends in the considered temperature range from the negative values of the total free energy of mixing ΔG_M. Optimization of the extent of intermolecular interactions between the two polymers in these blends is investigated. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Conductive polyaniline–polychloroprene blends

The electrical conductivity of polychloroprene (CR)/polyaniline (Pani) blends prepared by bulk and solution processes were investigated. Pani doped with HCl (Pani · HCl) and p-toluenesulfonic acid (Pani · TSA) were employed in vulcanized blends obtained by the bulk process. These blends showed an increase in the conductivity only for blend composition of CR/Pani = 50:50 wt %. At this composition, blends with Pani · HCl and Pani · pTSA presented conductivity values of 10⁻⁹ and 10⁻¹⁰ S · cm⁻¹, respectively. CR/Pani · HCl blend films prepared by the solution process displayed surface conductivity values of 10⁻⁴ S · cm⁻¹ with as low as 10–15 wt % of PAni · HCl. Surface analysis of these blends by X-ray photoelectron spectroscopy indicated no traces of the conductive additive. The surface composition was found to be exclusively constituted of CR. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1543–1549, 1998     

Miscibility of Crystalline/Amorphous/Crystalline Biopolymer Blends from PLLA/PDLLA/PHB with Additives

Miscibility of three biopolymers (PLLA, PDLLA and PHB) blends were investigated by POM, WAXD, FTIR, and DSC. DSC verified the thermal properties of biopolymer blend with PVAc as a compatibilizer, and TBC as plasticizer. Some change in glass transition temperature (T_g) of biopolymer blends from 60°C to 0.7°C. The spherulitic morphology of blend 9 changing by addition more PHB (50%), the results dendritic spherulites. The adding PHB to PLLA blends make certain shifting in the diffraction peak from 2 ? = 16.9° to 2 ? = 16.6° and the carbonyl group shifts from 1752 cm^?1 to 1732 cm^?1 in blends, demonstrating polar interactions between them.     

Thermal stabilization by polyols of β-xylanase from Bacillus amyloliquefaciens

Purified endo-β-1,4-xylanase of Bacillus amyloliquefaciens MIR 32 retained 100% of its activity after 4 days of incubation at 50°C. Sorbitol (400 mg cm⁻³) produced a 63-fold increase in the half-life of the enzyme at 65°C, which was only 29 min at this temperature in the absence of the polyol. This thermal stabilizing activity increased exponentially in respect to sorbitol concentration in the range 250–400 mg cm⁻³ and was dependent on the pH, showing a maximum at pH values between 5·25 and 8·0. The circular dichroism (CD) thermal scanning profile (50°C h⁻¹) at 224 nm showed that changes in the secondary structure of xylanase started at 65°C, while in the presence of sorbitol (400 mg cm⁻³) these modifications started at 80°C. This study indicated that sorbitol might be a valuable stabilizer for the use of β-xylanase from B. amyloliquefaciens at high temperatures. © 1998 SCI     

Miscibility of polymer blends of poly(styrene‐co‐4‐hydroxystyrene) with bisphenol‐A polycarbonate

The miscibility of blends of bisphenol‐A polycarbonate (BAPC) and tetramethyl bisphenol‐A polycarbonate (TMPC) with copolymers of poly(styrene‐co‐4‐hydroxystyrene) (PSHS) was studied in this work. It has been demonstrated that BAPC is miscible with PSHS over a region of approximately 45–75 mol % hydroxyl groups in the copolymer. TMPC has a wider miscible window than BAPC when blended with PSHS. The blend miscibility was considered to be driven by the intermolecular attractive interactions between the hydroxyl groups of the PSHS and the π electrons of the aromatic rings of both polycarbonates (PCs). As the FTIR measurements showed, after blending of BAPC with PSHS, there is no visible shift of the carbonyl band of BAPC at 1774 cm⁻¹, whereas the stretching frequency of the free hydroxyl groups of the copoly‐ mers at 3523 cm⁻¹ disappeared. The large positive values of the segment interaction energy density parameter B_st‐HS calculated from the group contribution approach indicated that the intramolecular repulsive interaction may also have played a role in the promotion of the blend miscibility. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 639–646, 1999     

Chemical modification of crosslinked phenyl acrylate copolymers with monoethanolamine

Copolymerisation of phenyl methacrylate, 4-chlorophenyl acrylate, 4-nitrophenyl acrylate and 2,4,6-tribromophenyl acrylate with divinyl benzene was carried out in aqueous suspension medium at 80°C using benzoyl peroxide as radical initiator. The resulting beaded copolymers were characterised by FTIR. optical and scanning electron microscopy. Polymer analogue reactions of these particulate copolymers with monoethanolamine were carried out at 60.80 and 100°C in dimethyl sulphoxide as solvent. The progress of the reactions was followed by observing the disappearance of phenyl ester carbonyl absorption at 1750 cm⁻¹ and the appearance of 1650cm⁻¹ vibration corresponding to the characteristic amide carbonyl. The percentage conversions were calculated, and the effect of polar substituents in the phenyl acrylates as well as temperature on the reaction are discussed.     

The Influence of Temperature and Composition on the Operation of Al Anodes for Aluminum‐Air Batteries

The influence of composition and temperature on the anode polarization and corrosion rate of pure Al and Al‐In anodic alloys in 8M NaON electrolyte has been investigated. High current density (more than 800 mA cm⁻²) and faradaic efficiency over 97% were observed for all investigated alloys at 60 °C. Lower temperature provides lower current density (200–300 mA cm⁻² at 40 °C, and less than 100 mA cm⁻² at 25 °C). Different formation of the product reaction layers was observed for pure aluminum and Al–0.41In alloy, leading to the different polarization character of the samples. The comparison of two Al‐In alloys with similar composition has been carried out. Al–0.45In alloy having a coarse‐grained structure had a more positive no‐current potential and lower value of anode limiting current (200 mA cm⁻² vs. 300 mA cm⁻²) compared with the fine‐grained Al–0.41In alloy, as well as greater parasitic corrosion rate and greater no‐current corrosion. The current‐voltage, power and discharge characteristics of the aluminum‐air cell with Al–0.41In anode and gas diffusion cathode have been investigated. Open circuit voltage of the cell is 1.934 V and the maximum power density of the cell is 240 mW cm⁻² at the voltage of 1.3 V.     

Phosphorus-Containing polyurethanes based on bisphenol-AF,prepared by N-alkylation

Phosphorus-containing polyurethanes (PU-P) based on bisphenol-AF were synthesized by N-alkylation in a two-step process. First, the polymer was metalated with sodium hydride; then the prepared urethane polyanion was treated with diethyl 2-bromoethyl phosphate. IR spectra exhibited characteristic absorptions at 1303 cm⁻¹ (PO stretch), 1015 cm⁻¹ (CH stretch), 1646 cm⁻¹ (CO stretch), 1231 cm⁻¹ (CNH), and 1053 cm⁻¹ (CO O C stretch). In the ¹H-NMR spectrum of the maximum substituted PU-P, the signal of the urethane proton (NH  CO O) at 9.87 ppm virtually disappeared as expected; new signals appeared at 1.20–1.24 ppm (POCH₂CH ₃) and 3.79 ppm (POCH ₂CH₃). Physical and thermal properties of the N-alkylated polymer were also investigated with differential scanning calorimetry (DSC), solubility, X-ray diffraction, thermogravimetric analysis (TGA), limiting oxygen index (LOI), and reduced viscosity. DSC analysis showed that T_g values were decreased from 81 to 43°C. The reduced viscosities of the PU-Ps were observed in the range of 0.23–0.18 dL g⁻¹. The results of TGA revealed that the thermal stability was decreased, because the phosphorus moiety in the PUs is readily dissociated thermally. The PU-Ps exhibited enhanced fire resistance because phosphorus simultaneously promoted carbonization of the polymer and inhibited combustion. The X-ray diffraction patterns of the PU-Ps showed that with increasing phosphorus content, the degree of crystallinity of the PUs decreased. N-alkylated PUs are soluble, not only in polar solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and H₂SO₄, but also in less polar solvents such as phenol, toluene, THF, and trichloroethylene. © 1996 John Wiley & Sons, Inc.     

The phase behavior and thermal stability of blends of poly(styrene‐co‐methacrylic acid)/poly(styrene‐co‐ 4‐vinylpyridine)

The hydrogen bonding and miscibility behaviors of poly(styrene‐co‐methacrylic acid) (PSMA20) containing 20% of methacrylic acid with copolymers of poly(styrene‐co‐4‐vinylpyridine) (PS4VP) containing 5, 15, 30, 40, and 50%, respectively, of 4‐vinylpyridine were investigated by differential scanning calorimetry, thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). It was shown that all the blends have a single glass transition over the entire composition range. The obtained T_gs of PSMA20/PS4VP blends containing an excess amount of PS4VP, above 15% of 4VP in the copolymer, were found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are able to form interpolymer complexes. The FTIR study reveals presence of intermolecular hydrogen‐bonding interaction between vinylpyridine nitrogen atom and the hydroxyl of MMA group and intensifies when the amount of 4VP is increased in PS4VP copolymers. A new band characterizing these interactions at 1724 cm⁻¹ was observed. In addition, the quantitative FTIR study carried out for PSMA20/PS4VP blends was also performed for the methacrylic acid and 4‐vinylpyridine functional groups. The TGA study confirmed that the thermal stability of these blends was clearly improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Hyperbranched Poly(Glycidol)-Grafted Silica Nanoparticles for Enhancing Li-Ion Conductivity of Poly(Ethylene Oxide)

Silica nanoparticles bearing hyperbranched polyglycidol (hbP) grafts are synthesized and blended with poly(ethylene oxide) (PEO) for the fabrication of composite solid polymer electrolytes (SPEs) for enhancing Li-ion conductivity. Different batches of hbPs are prepared, namely, the 5th, 6th, and 7th with increasing molecular weights using cationic ring-opening polymerization and grafted the hbPs onto the silica nanoparticles using quaternization reaction. The effect of end functionalization of hbP-grafted silica nanoparticles with a nitrile functional group (CN–hbP–SiO₂) on the ionic conductivity of the blends with PEO is further studied. High dipole moments indicate polar nature of nitriles and show high dielectric constants. Among all the hbPs, the 6th-batch CN–hbP–SiO₂ nanoparticles exhibit better ionic conductivity on blending with PEO showing ionic conductivity of 2.3 × 10⁻³ S cm⁻¹ at 80 °C. The blends show electrochemical stability up to 4.5 V versus lithium metal.     

Rapid FTIR method for quantification of styrene‐butadiene type copolymers in bitumen

The mid‐IR molar absorptivity for polystyrene (PS) and polybutadiene (PB) blocks were obtained for five styrene‐butadiene‐styrene (SBS) and SB copolymers, including linear, branched, and star copolymers, and their blends with bitumen. The average absorptivity for PS and PB blocks was 277 and 69 L mol⁻¹ cm⁻¹ and it was little affected by the S/B ratio or the copolymer architecture. In the presence of bitumen, Beer's law was obeyed but the respective PS and PB absorptivity was 242 and 68 L mol⁻¹ cm⁻¹, possibly because of weak interactions between the copolymer and bitumen. The absorptivity values were used to calculate the concentration of SB‐type copolymers in blends with bitumen with an accuracy of 10% or better. The method can be used to probe the stability of bitumen–copolymer blends in storage at 165°C, to determine the copolymer concentration in commercial polymer modified bitumen (PMB), and to assess the resistance of PMB to weathering. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1034–1041, 2001     

Investigation on the Thermal Expansion and Theoretical Density of 1,3,5‐Trinitro‐1,3,5‐Triazacyclohexane

The CTE and the theoretical density are important properties for energetic materials. To obtain the CTE and the theoretical density of 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), XRD, and Rietveld refinement are employed to estimate the dimensional changes, within the temperature range from 30 to 170 °C. The CTE of a, b, c axis and volume are obtained as 3.07×10⁻⁵ K⁻¹, 8.28×10⁻⁵ K⁻¹, 9.19×10⁻⁵ K⁻¹, and 20.7×10⁻⁵ K⁻¹, respectively. Calculated from the refined cell parameters, the theoretical density at the given temperature can be obtained. The theoretical density at 20 °C (1.7994 g cm⁻³) is in close match with the RDX single‐crystal density (1.7990 g cm⁻³) measured by density gradient method. It is suggested that the CTE measured by XRD could perfectly meet with the thermal expansion of RDX.     

Assessing the Effects of Sunlight on the Photooxidation of Tropical Oils with Experimental and Computational Approaches

This study aims to investigate the influence of high-intensity sunlight radiation on the photooxidation of tropical oils (TO). Coconut oil (CNO), palm oil (PO), and palm kernel oil (PKO) were chosen for determining the indicators of photooxidation when exposed to and in the absence of sunlight for 7 weeks. The results showed a significant (P < 0.05) increase in free fatty acid (FFA) levels and peroxide value (PV) when the TO were exposed to sunlight. The iodine value and color content decreased significantly (P < 0.05) due to the decomposition of unsaturated FFA owing to the breaking down of the π-bonds and the degradation of color pigments during photooxidation. Fourier transform infrared spectroscopy (FTIR) analysis showed strong vibrational absorptions at 1721 and 3505 cm⁻³, 1720 and 3560 cm⁻³, and 1721 and 3554 cm⁻³ for the CNO, PO, and PKO samples exposed to sunlight, respectively. These bands can be attributed to the presence of secondary oxidation products, which were absent in the TO that were not exposed to sunlight. A simulation was performed to support the FTIR results, which also indicated peaks from the secondary oxidation products at 1744 and 3660 cm⁻³. The study also revealed that the rate of photooxidation was different for each TO. The rate of oxidation followed the order PO > PKO > CNO. In contrast, no notable changes were observed in the TO kept away from sunlight. These results suggest that exposing TO to sunlight influences their oxidation stability and quality.     

Thermooxidative degradation of poly(vinyl chloride)/acrylonitrile–butadiene–styrene blends

The thermal degradation process of poly(vinyl chloride)/acrylonitrile–butadiene–styrene (PVC/ABS) blends was investigated by dynamic thermogravimetric analysis in the temperature range 50–650°C in air. The thermooxidative degradation of PVC/ABS blends of different composition takes place in three steps. In this multistep process of degradation the first step, dehydrochlorination, is the most rapid. The maximal rate of dehydrochlorination for the PVC blends containing up to 20% ABS-modifier is achieved at average conversions of 23.5–20.0%, i.e., at 13.5% for the 50/50 blend. The apparent activation energies (E = 103–116 kJ mol⁻¹) and preexponential factors (Z = 2.11 × 10⁹−3.45 × 10¹⁰min⁻¹) for the first step of the degradation process were calculated after the Kissinger method. © 1996 John Wiley © Sons, Inc.     

Rate of imidization of polymerizable reaction mixtures: PMR-15

Imidization of PMR-15 was investigated using Fourier transform infrared spectroscopy (FTIR) as a function of time and temperature. Imidization was performed at 65 ≤ T ≤ 300°C for 3 ≤ t ≤ 150 min. FTIR spectroscopy showed that imidization (measured by the changes in the imide carbonyl absorption at 1778 cm⁻¹) increased with temperature and time. Imidization was found to be nearly completed in 2.5 h at 300°C. Imidization of PMR-15 occurred in three stages: (i) the initial imidization region characterized by gradual reaction followed by (ii) a very rapid reaction region that spans about 0.5 h and (iii) a final imidization region characterized by a gradual reaction and spans about 2 h. An Avrami-type kinetic analysis was used to obtain the reaction order of 1.5 and 1.7 and the rate constant for imidization of 1.3 × 10⁻³ and 1.5 × 10⁻³ min^−3/2; at 135 and 165°C, respectively. Comparison with other kinetic models shows agreement at low conversions (p ≤ 15%). At high conversions of p > 20%, a second-order kinetic model seems to fit the data reasonably well in agreement with the observed order. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2529–2538, 1997     

Synthesis and Electrochemical Properties of BaFe1−xCuxO3−δ Perovskite Oxide for IT‐SOFC Cathode

A series of iron‐based perovskite oxides BaFe_1−xCu_xO_3−δ (x = 0.10, 0.15, 0.20 and 0.25, abbreviated as BFC‐10, BFC‐15, BFC‐20 and BFC‐25, respectively) as cathode materials have been prepared via a combined EDTA‐citrate complexing sol‐gel method. The effects of Cu contents on the crystal structure, chemical stability, electrical conductivity, thermal expansion coefficient (TEC) and electrochemical properties of BFC‐x materials have been studied. All the BFC‐x samples exhibit the cubic phase with a space group Pm3m (221). The electrical conductivity decreases with increasing Cu content. The maximum electrical conductivity is 60.9 ± 0.9 S cm⁻¹ for BFC‐20 at 600 °C. Substitution of Fe by Cu increases the thermal expansion coefficient. The average TEC increases from 20.6 × 10⁻⁶ K⁻¹ for BFC‐10 to 23.7 × 10⁻⁶ K⁻¹ for BFC‐25 at the temperature range of 30–850 °C. Among the samples, BFC‐20 shows the best electrochemical performance. The area specific resistance (ASR) of BFC‐20 on SDC electrolyte is 0.014 Ω cm² at 800 °C. The single fuel cell with the configguration of BFC‐20/SDC/NiO‐SDC delivers the highest power density of 0.57 W cm⁻² at 800 °C. The favorable electrochemical activities can be attributed to the cubic lattice structure and the high oxygen vacancy concentration caused by Cu doping.     

Metal adhesive properties of polyamides having the 2,3‐bis(1,4‐phenylene)quinoxalinediyl structure

Polyamides were synthesized by interfacial polycondensation of 2,3‐bis(4‐chloroformylphenyl)quinoxaline (BCFPQ) and several aliphatic diamines using a phase transfer catalyst, and their adhesive property for stainless steel was investigated. The inherent viscosity of the obtained polyamides ranged from 0.37 to 1.24 dL g⁻¹. The glass transition temperatures of the polyamides ranged between 154 and 201°C, and their thermal decomposition temperatures were above 450°C. The polyamides were soluble in several organic solvents, including m‐cresol, N‐methyl‐2‐pyrrolidone (NMP), and formic acid. The adhesive property for stainless steel was examined by a standard tensile test. One member of the series, polyamide P8, derived from BCFPQ and 1,8‐octanediamine, displayed high tensile strength with values of 232 kgf cm⁻² at 20°C, 173 kgf cm⁻² at 120°C, and 137 kgf cm⁻² at 180°C. Thus, the tensile strength of P8 decreased at 180°C, but the decrease was much smaller than that of an epoxy resin in wide use as a metal adhesive. Heat distortion temperature, measured by thermal mechanical analysis, of P8 was 191°C. This suggested that P8 possessed high thermal resistance in metal adhesives. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1366–1370, 1999     

Chemical copolymerization of aniline with o‐chloroaniline: thermal stability by spectral studies

Poly(aniline‐co‐o‐chloroaniline) salts were synthesized by chemical copolymerization of aniline with o‐chloroaniline using three different acids. The polymer salt samples were heat treated at four different temperatures (150, 200, 275 and 375 °C) and the thermal stability of the polymer salts were studied by conductivity, electron paramagnetic resonance (EPR), infrared (IR) and electronic absorption spectral measurements. The conductivity of the copolymers could be controlled in a broad range from 10 S cm⁻¹ for homopolymer of aniline to 10⁻⁴ S cm⁻¹ for those of o‐chloroaniline. No structural changes took place up to 200 °C and this was confirmed from EPR, IR and electronic absorption spectra. No definite correlation exists between conductivity and spin concentration. © 2000 Society of Chemical Industry     

Effect of isothermal aging on the imidization of PMR-15

The imidization of polymerizable reactive mixtures, PMR-15 has been performed in a vacuum oven at isothermal aging temperatures ranging from 65 to 200°C for aging periods of 0.5 to 2.5 h. The weight loss of the resin and chemical changes that occurred as a result of aging were monitored gravimetrically and by FT-IR spectroscopy. Differential scanning calorimetry was used to determine the temperature at which imidization took place. Imidization was observed to commence at 65°C after long aging times, t ≥ 2.5 h and at ∼95°C at a shorter time, t ∼0.5 h. At higher aging temperatures of 135 to 165°C, extensive imidization occurred. This was shown by the dramatic increase in imide absorption bands at 1780 and 1380 cm⁻¹. Beyond 165°C, there were no significant changes in the imide absorption bands, suggesting that imidization was nearly complete. The activation energy for isothermal aging was determined from the slope of the log of the rate of weight loss vs 1/T curve to be ∼4.5 kJ/mol and is lower than the average activation energy for imidization ∼43 kJ/mol obtained from the plot of the log of the rate of increase of the imide carbonyl peak absorption at 1780 cm⁻¹ vs 1/T.