Fractal crystal growth of poly(ethylene oxide) crystals from its amorphous monolayers

The fractal crystal growth process of the PEO monolayer with a molecular weight and a distribution has been followed on the substrate of the silicon wafer using AFM equipped with a hot stage. A depletion zone between the ramified crystals and the viscous amorphous layer was found in the AFM height images. The formation of the depletion zone shows that the molecules have to “break up” with the amorphous layer and then diffuse through the depletion zone to join the crystals. The diffusion process further means the diffusion-controlled mechanism resulting in the fractal crystal pattern with a fractal dimension D_f ≈ 1.63. The linear feature of the crystal pattern radius growth with time means that the surface kinetic process plays a key role in the crystal growth.     

Synthesis, characterization and thermodynamic properties of poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone)

Poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone) P(MHPMA-co-VP) was synthesized in 1, 4-dioxane solution using benzoyl peroxide (BPO) as initiator at 60 °C. The copolymer was characterized by ¹H ¹³C NMR, FT-IR, DSC, TGA, size exclusion chromatography analysis (SEC) and elemental analysis techniques. According to SEC, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of PMHPMA-co-VP were found to be 58,000, 481,000 g/mol and 8.26, respectively. According to TGA, carbonaceous residue value of PMHPMA-co-VP was found to be 6% at 500 °C. Also, some thermodynamic properties of PMHPMA-co-VP such as the adsorption enthalpy, ΔH_a, molar evaporation enthalpy, ΔH_v, the sorption enthalpy, , sorption free energy, , sorption entropy, , the partial molar free energy, , the partial molar heat of mixing, , at infinite dilution was determined for the interactions of PMHPMA-co-VP with selected alcohols and alkanes by inverse gas chromatography (IGC) method in the temperature range of 323-463 K. According to the specific retention volumes, , the weight fraction activity coefficients of solute probes at infinite dilution, , and Flory-Huggins interaction parameters, between PMHPMA-co-VP-solvents were determined in 413-453 K. According to and , selected alcohols and alkanes were found to be non-solvent for PMHPMA-co-VP at 413-453 K. The glass transition temperature, T_g, of the PMHPMA-co-VP found to be 370 and 363 K, respectively, by IGC and DSC techniques, respectively.     

Melt processed blends of poly(styrene-co-acrylonitrile) and poly(phenylene ether) compatibilized with polystyrene-b-polybutadiene-b-poly(methyl methacrylate) triblock terpolymers

Polystyrene-b-polybutadiene-b-poly(methyl methacrylate) triblock terpolymers (SBM) with equal (symmetric) and different (asymmetric) block lengths were used to compatibilize polymer blends based on poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN). First, the rheological behavior of the individual components and their binary mixtures was investigated. Based on the results, samples of PPE, SAN and SBM in weight ratios of 32/48/20 were melt blended and the morphology development during melt processing was investigated. It was found that a raspberry morphology, i.e. dispersion of PPE in SAN with rubbery PB domains at the PPE/SAN interface, could be achieved with a symmetric SBM with under sufficiently high shear rate, while a symmetric SBM with did not yield the desired morphology. Asymmetric SBMs with long PS blocks dissolved in the PPE phase did not display the expected compatibilization effect. In order to obtain a raspberry morphology with asymmetric copolymers it is suggested to pre-blend the SBM with SAN before adding the PPE. Finally it is shown that a commercial PPE containing High Impact Polystyrene (HIPS) as a toughness modifier can be compatibilized with SAN by melt processing using a symmetric SBM triblock terpolymer with      

Electrochemical performances of gel polymer electrolytes using tetra(ethylene glycol) diacrylate

A gel polymer electrolyte (GPE) was prepared using tetra(ethylene glycol) diacrylate monomer, benzoyl peroxide, and (). The LiCoO₂/GPE/graphite cells were prepared and their electrochemical properties were evaluated at various current densities and temperatures.The viscosity of the precursor containing the tetra(ethylene glycol) diacrylate monomer was around . The ionic conductivity of the gel polymer electrolyte at 20°C was around . The gel polymer electrolyte had good electrochemical stability up to vs. Li/Li⁺. The capacity of the LiCoO₂/GPE/graphite cell at rate was 63% of the discharge capacity at rate. The capacity of the cell at −10°C was 81% of the discharge capacity at 20°C. Discharge capacity of the cell with gel polymer electrolyte was stable with charge-discharge cycling.     

Miscibility with positive deviation in Tg-composition relationship in blends of poly(2-vinyl pyridine)-block-poly(ethylene oxide) and poly(p-vinyl phenol)

Phase behavior and miscibility with positive deviation from linear T_g-composition relationship in a copolymer/homopolymer blend system, poly(2-vinyl pyridine)-block-poly(ethylene oxide) (P2VP-b-PEO)/poly(p-vinyl phenol) (PVPh), were investigated by differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR) and solid-state ¹³C nuclear magnetic resonance (¹³C NMR), optical microscopy (OM), and scanning electron microscopy (SEM). Optical and electron microscopy results as well as NMR proton spin-lattice relaxation times in laboratory frame () all confirmed the miscibility as judged by the T_g criterion using DSC. In comparison to the literature result on a homopolymer/homopolymer blend of P2VP/PVPh, fitting with the Kwei equation on the T_g-composition relationship for the block-copolymer/homopolymer blend of P2VP-b-PEO/PVPh blend system yielded a smaller q value (q = 120) for P2VP-b-PEO/PVPh than that for P2VP/PVPh blend (q = 160). The FT-IR and ¹³C NMR results revealed hydrogen-bonding interactions between the pendant pyridine group of P2VP-b-PEO and phenol unit in PVPh, which is responsible for the noted positive deviation of the T_g-composition relationship. Comparison of the shifts of hydroxyl IR absorbance band, reflecting the average strength of H-bonding, indicates a decreasing order of P2VP/PVPh > P2VP-b-PEO/PVPh > PEO/PVPh blends. The PEO block in the copolymer segment tends to defray the interaction strength in the P2VP-b-PEO/PVPh blends because of relative weaker interaction between PEO and PVPh than that between P2VP and PVPh pairs. A comparative ternary (P2VP/PEO)/PVPh blend was also studied as the controlling experiments for comparison to the P2VP-b-PEO/PVPh blend. The thermal behavior and interaction strength in (P2VP/PEO)/PVPh ternary blends are discussed with those in the P2VP-b-PEO/PVPh copolymer/homopolymer blend.     

Physicochemical characterization of poly(tert-butyl acrylate-b-methyl methacrylate) prepared with atom transfer radical polymerization by inverse gas chromatography

Poly(tert-butyl acrylate) (PtBuA) was synthesized by atom transfer radical polymerization (ATRP) using methyl-2-bromo propionate (MBP) as an initiator in bulk at 80 °C. The successive ATRP of methyl methacrylate in diphenyl ether at 80 °C using previously obtained PtBuA as a macroinitiator led to formation of poly(tert-butyl acrylate-b-methyl methacrylate) (poly(tBuA-b-MMA)). The synthesized macroinitiator and block copolymer have controlled molecular weight and low polydispersity (M_w/M_n<1.2). The block copolymer was characterized by gel permeation chromatography (GPC) and ¹H NMR. The retention diagrams of poly(tBuA-b-MMA) for some aliphatic esters and aromatic hydrocarbons were obtained using inverse gas chromatography (IGC) technique. The glass transition temperatures, T_gs of poly(tBuA-b-MMA) were determined by both differential scanning calorimeter (DSC) and IGC. It was observed that the block copolymer represents three T_gs at 50, 75 and 100 °C by IGC although it represents only one T_g at 71 °C by DSC. After the column was quenched from 180 to 0 °C, the T_g at 100 °C shifted to 105 °C however others did not change. Specific retention volumes, and the thermodynamical polymer-solvent interaction parameters such as Flory-Huggins, , equation-of-state, and effective exchange energy, X_eff were found for all studied solvents. Partial molar heat of sorption, , partial molar heat of mixing, and molar heat of vaporization, ΔH_v, were determined. In addition, the solubility parameter of the corresponding block copolymer, δ₂ was determined as 11.0 (cal/cm³)^1/2 at 25 °C.     

Crystallization of a miscible propylene/ethylene copolymer blend

The crystallization behavior and morphological patterns of a miscible blend of two propylene/ethylene (P/E) copolymers that differed in ethylene content were studied. Metallocene-catalyzed P/E copolymers containing 3.1 and 11.0 mol% ethylene were chosen for blending. The difference in ethylene content was small enough to ensure miscibility of the pair in the melt, and the ethylene content was low enough to ensure that both were crystallizable. The blends were characterized by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), optical microscopy (OM) and atomic force microscopy (AFM). The complex melting endotherm of the blends consisted of a broad low temperature peak at T_m1, a high temperature peak at T_m2, and an intermediate peak at which was not characteristic of either constituent and depended on blend composition. The multiple melting peaks arose from distinct crystal populations. All the blends exhibited a mixed morphological texture of α-radial lamellae with short, densely packed γ-overgrowths, interspersed with areas of α-crosshatch. The high temperature peak at T_m2 was assigned to the melting of the α-radial lamellae which formed from chains of the lower comonomer constituent. The broad low temperature peak at T_m1 was attributed to the melting of γ-crystal overgrowths on the radial lamellae. The new peak at was thought to arise from the melting of the α-crosshatch lamellae. The lamellar thickness, and hence , correlated with the crystallization temperature, which decreased as the blend was made richer in the higher comonomer constituent.     

Poisoning effect of CO on ethylene polymerization with Ni(II)-diimine/MAO

CO was not a comonomer but an inhibitor in ethylene polymerization catalyzed over [1,2-bis(2,6-diisopropylphenylimino)]acenaphthene nickel(II) dibromide (1)/MAO. The average number of active sites, , and the average rate constant for chain propagation, of the (1)/MAO system was determined using CO inhibition method based on the assumption that two molecules of CO coordinate to each active center. At 0 °C, the average number of active centers, , was increased with the Al/Ni ratio, and , was not influenced by the Al/Ni ratio. Up to Al/Ni ratio of 3000, the average number of active sites was saturated. Single active site was present at the high ratio of Al/Ni and its reactivity with CO is uniform at 0 °C. The maximum average activity was 5262.07 (kg-PE/mol-Ni/atm/hr) and 65.7% of (1) was converted to form active cation complexes at 0 °C and Al/Ni molar ratio of 5000, while 36.5% of (1) was activated at the Al/Ni molar ratio of 250. Above 30 °C, the complicated CO poisoning behavior was observed because the reactivity and stoichiometry of active centers with CO were not uniform and their thermal stability was very poor.     

Crystallization, melting, and morphology of a poly(ethylene oxide) diblock copolymer containing a tablet-like block of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene}

A poly(ethylene oxide) diblock copolymer containing a short block of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PEO-b-PMPCS) has been successfully synthesized via atom transfer radical polymerization (ATRP) method. The number average molecular weights (M_n) of the PEO and PMPCS blocks are 5300 and 2100 g/mol, respectively. Combining the techniques of differential scanning calorimetry (DSC), optical microscopy (OM), wide angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS), we have found that the PMPCS blocks, which are tablet-like, can significantly affect the crystallization and melting of the diblock copolymer. The sample studied can form the crystals with a monoclinic crystal structure identical to that of the homo-PEO. The melting temperature (T_m) of the diblock copolymer increases monotonically with crystallization temperature (T_c), which is remarkably similar to the behavior of long period. On the basis of Gibbs-Thomson relationship, the equilibrium T_m of the diblock copolymer is estimated to be 65.4 °C. In a wide undercooling (ΔT) range (14 °C<ΔT<30 °C), the isothermal crystallization leads to square-shaped crystals. The PEO-b-PMPCS crystallization exhibits a regime I→II transition at ΔT of 19 °C. The PEO blocks are non-integral folded (NIF) in the crystals, and the PMPCS blocks rejected to lamellar fold surfaces prevent the NIF PEO crystals from transforming to integral folded (IF) ones. Furthermore, the PMPCS tablets may adjust their neighboring positions up or down with respect to the lamellar surface normal, forming more than one PMPCS layer to accompany the increase in the PEO fold length with increasing T_c.     

Influence of carbon dioxide partial pressure and fluidization velocity on activated carbons prepared from scrap car tyre in a fluidized bed

The effect of carbon dioxide partial pressure and fluidization velocity on activated carbons produced by carbon dioxide activation of scrap car tyre rubber in a fluidized bed has been studied. The method consisted of carbonization at under nitrogen followed by activation at . Three types of activated carbons were produced using activated gas concentrations of 20, 60 and 100% carbon dioxide by volume, the rest nitrogen, at a constant fluidization velocity (0.0393 m/s) to investigate the influence of carbon dioxide partial pressure. Within the experimental setup and activation time of 4 h, it was observed that BET surface area and total pore volume increased with carbon dioxide partial pressure reaching and , respectively, for 100% activation with carbon dioxide. Three other types of activated carbons were produced using 100% carbon dioxide at two (0.0393 m/s), three (0.0589 m/s) and four (0.0786 m/s) times the minimum fluidization velocity (U_mf). The BET surface area and total pore volume were observed to increase with fluidization velocity (which can be viewed as an indicator of the intensity of mixing in the bed), reaching and , respectively, at four times the minimum fluidization velocity.     

Kinetics of water sorption on SWS-1L (calcium chloride confined to mesoporous silica gel): Influence of grain size and temperature

Kinetics of water sorption on loose grains of composite sorbent CaCl₂ confined to mesoporous silica (SWS-1L) was measured at and over water uptake range 0-0.47 g/g for various particle sizes R_p (between 0.355 and 1.4 mm). The measurements were performed in a constant pressure unit based on a CAHN microbalance under isothermal external conditions.The results obtained evidence an enhancement of the sorption rate and apparent diffusion constant with the decrease in the particle size (approximately as at ). Contribution of thermal effects was found for water sorption on smaller SWS particles (0.355-0.425 mm), which decreases the sorption rate.The apparent water diffusivity was found to depend on the local slope of the SWS water sorption isotherm. The pore diffusivity of water in the temperature range 33-69 °C was calculated from experimental data that is approximately 10 times lower than the Knudsen pore diffusivity estimated for pores of silica KSK. The possible reasons of the diffusivity reduction are discussed.     

Effect of N(4)-substituent groups on transfer of 2-benzoylpyridine thiosemicarbazone derivates at the water/1,2-dichloroethane interface

Dependent on the pH of the aqueous phase, the transfer of protonated forms of 2-benzoylpyridine N(4)-phenyl thiosemicarbazone (BPPT) (which has antimicrobial, antifungal and anticytotoxic activities) and 2-benzoylpyridine N(4)-ethyl thiosemicarbazone (BPET) across water/1,2-dichloroethane (1,2-DCE) interface has been studied by cyclic voltammetry. The protonation constants of the ligands ( and ) were determined by spectrophotometry. The standard partition coefficients () and the standard Gibbs energies of ionic (cationic) species of ligands () were calculated from the standard transfer potentials (). The standard Gibbs energies of their transfer () and partition coefficients of neutral species (log P_N) were determined by shake-flask method. These thermodynamic parameters were evaluated as a quantitative and qualitative measure of the lipophilicities of two compounds. The differences between the partition coefficients of cationic and neutral form of compounds [diff(log PI⁺−N)] were interpreted by results obtained from voltammetric data. Effect of N(4)-phenyl and ethyl groups for transfer of 2-benzoylpyridine thiosemicarbazone derivatives at macro-liquid/liquid interface was investigated. The antimicrobial activity of BPET was tested against four types of bacteria and found to be active against Staphlylococcus aureus.     

Syntheses and specific interactions of poly(hydroxyethyl methacrylate-b-vinyl pyrrolidone) diblock copolymers and comparisons with their corresponding miscible blend systems

Combination of atom transfer radical and conventional free radical polymerizations has been successfully used to prepare poly(hydroxyethyl methacrylate-b-vinyl pyrrolidone) (PHEMA-b-PVP) copolymers with controlled molecular weight and low polydispersity (<1.4). The thermal behavior and specific interaction of PHEMA-b-PVP diblock copolymers and their corresponding PHEMA/PVP blends were characterized. The result shows that glass transition temperatures of diblock copolymers analysed by differential scanning calorimetry (DSC) are higher than those of the blends. Infrared and solid-state NMR spectroscopic analyses show that hydrogen-bonding interaction of hydroxyl-carbonyl groups of diblock copolymers was also greater than that of the blends. Measurement of the proton spin-lattice relaxation time in the rotating frame, , reveals that all diblock copolymers and blends possess one composition-dependent , indicating that both diblock copolymers and blends are homogeneous, which is consistent with the DSC analysis.     

Crystal structure analysis of cylindrical phase of polystyrene-b-polyethylenebutylene-b-polystyrene triblock copolymer

Crystal structure analysis of cylindrical phase of polystyrene-b-polyethylenebutylene-b-polystyrene triblock polymer was carried out. One cylinder with radius 74.20 Å passes through a hexagonal unit cell with c=∞, β=120°. The temperature factor which reflects the disorder of the cylinder is 14,525 and 〈Δr²〉^1/2 is estimated as 13.56 Å. This suggests that the cylinder is distorted and the surface of the cylinder is disordered.