Properties and crystallization kinetics of poly(ether ether ketone)‐co‐poly(ether ether ketone ketone) block copolymers

A series of block copolymers composed of poly(ether ether ketone) (PEEK) and poly(ether ether ketone ketone) (PEEKK) components were prepared from their corresponding oligomers via a nucleophlilic aromatic substitution reaction. Various properties of the copolymers were investigated with differential scanning calorimetry (DSC) and a tensile testing machine. The results show that the copolymers exhibited no phase separation and that the relationship between the glass‐transition temperature (T_g) and the compositions of the copolymers approximately followed the formula T_g = T_g1X₁ + T_g2X₂, where T_g1 and T_g2 are the glass‐transition‐temperature values of PEEK and PEEKK, respectively, and X₁ and X₂ are the corresponding molar fractions of the PEEK and PEEKK segments in the copolymers, respectively. These copolymers showed good tensile properties. The crystallization kinetics of the copolymers were studied. The Avrami equation was used to describe the isothermal crystallization process. The nonisothermal crystallization was described by modified Avrami analysis by Jeziorny and by a combination of the Avrami and Ozawa equations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1652–1658, 2005     

Fabrication of suspended carbon microstructures by e-beam writer and pyrolysis

A fabrication process has been developed to create suspended carbon microelectromechanical system (C-MEMS) structures. SU-8, a negative photoresist, was used as the starting material and was converted to the desired carbon microstructures using pyrolysis in an inert atmosphere. Suspended carbon-micro and nano electromechanical system (C-MEMS/NEMS) structures with feature sizes down to 500 nm were fabricated by ultra violet/electron beam (EB) lithography and pyrolysis. The problem of charging of the non-conductive SU-8 surface was solved by partially masking a thin metal layer to prevent the repulsion of negative charged electrons before EB writing. Complex suspended C-MEMS structures, such as bridges and networks have been formed. This fabrication method can accurately and reproducibly produce various suspended C-MEMS structures which have applications in microelectronics and biosensing.     

Crystallization kinetics of low‐density polyethylene and polypropylene melt‐blended with a low‐Tg tin‐based phosphate glass

The nonisothermal and isothermal crystallizations of low‐density polyethylene (LDPE) and polypropylene (PP) in phosphate glass (Pglass)–polymer hybrid blends were studied through differential scanning calorimetry (DSC). As the Pglass volume fraction was increased, the percentage crystallinity decreased. The half‐time for crystallization decreased as the propagation rate constant rose, for both of the polymer matrices, with increasing Pglass concentrations. The Pglass was observed to be a nucleating agent for formation of two‐ or three‐dimensional spherulites in the hybrids. Tensile modulus improved for both of the Pglass–polymer hybrids up to 40% Pglass, but the energy to break decreased. Tensile strength changed slightly with the addition of Pglass to the LDPE matrix, exhibiting a larger value than that of pure LDPE at 30%. The tensile strength decreased as more Pglass was added to the PP matrix. The observed differences between tensile properties of the Pglass–PP and Pglass–LDPE hybrids at identical Pglass volume concentration were found to be consistent with that of the crystallization behavior of the hybrids. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3445–3456, 2003     

A comparison of atomic force microscope friction and phase imaging for the characterization of an immiscible polystyrene/poly(methyl methacrylate) blend film

Three different forms of atomic force microscope (AFM) measurement, topography, friction force and phase imaging, have been used to investigate the surface morphology and local composition of an immiscible polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend film. This sample forms discrete, micron-size domains in a continuous matrix, which is attributed to the segregation of PMMA in PS. When the samples were imaged in air, contrast in friction and phase images was caused by variations in sample topography only. When the samples were imaged under water, however, both friction and phase imaging yielded non-topographic contrast between domains. We ascribe the contrast in both of these imaging modes to preferential softening of the hydrophilic, PMMA-rich domains and to stronger tip-sample adhesive forces, highlighting the AFM's utility for probing local elastic properties and for compositional mapping of soft polymer samples.     

Synthesis of copolymers of tert‐butyl vinyl ether with maleic and citraconic anhydrides

In the present study, the effects of charge‐transfer complex formation and intramolecular fragmentation (side‐chain lactonization) in radical copolymerization of tert‐butyl vinyl ether (t‐BVE) with anhydrides of maleic (MA) and citraconic (CA) acids and the structure–thermal behavior relationships of the resulting copolymers were examined using the ¹H‐NMR, FTIR, DSC, and TGA analysis methods. It was shown that copolymerization under the chosen conditions proceeded through intramolecular fragmentation with the formation of γ‐lactone units. Side‐chain fragmentation of t‐BVE–MA and t‐BVE–CA copolymers also was confirmed by TGA and DSC analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2455–2463, 2006 2006     

TGA analysis of γ‐irradiated linear low‐density polyethylene

Linear low‐density polyethylene (LLDPE), based on butene‐1 or hexene‐1, was irradiated with γ‐rays under vacuum or in the presence of air. The study focused on the influence of the dose rate and the γ‐dose on the thermal properties of LLDPE. Differential scanning calorimetry, thermogravimetric analysis (TGA), and TGA/FTIR techniques were used to address the thermal behavior as a result of γ‐irradiation. During this irradiation, competition between crosslinking and scission reactions, subsequent to oxidation reactions, occurred in the polymeric material, which strongly depends on the experimental conditions. A decrease of the crystallinity for γ‐irradiated samples was observed in particular for samples irradiated under vacuum. This observation may be explained by increased hindrance of segment mobility due to crosslinking reactions that prevent crystal growth. TGA investigations revealed an enhancement of the thermal stability for samples irradiated under vacuum but not for those irradiated in air. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2790–2795, 2006     

Fabrication and amplification of Rhodamine B‐doped step‐index polymer optical fiber

A step‐index polymer optical fiber (SI POF) containing Rhodamine B in poly(methyl methacrylate) (PMMA) has been fabricated by a preform technique. Fluorescence of different fiber lengths were observed and discussed. A high gain (23 dB) for a SI POF with 60‐cm length, 400‐μm diameter was obtained. The Rhodamine B content of the doped SI POF is 5 ppm‐wt. The signal wavelength providing the highest gain for a 60 cm SI POF is around 630 nm, and the optimum fiber length is about 60 cm at 10 kW launched pump power. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 681–685, 2004     

D.s.c. investigation of the states of water in poly(vinyl alcohol-co-itaconic acid) membranes

The state of water in water-swollen poly(vinyl alcohol-co-itaconic acid) membranes, having various water contents from 0.31 to 0.83, was investigated by d.s.c. measurements and compared with those in water-swollen poly(vinyl alcohol) membranes. The amount of freezing water in the membranes was estimated by use of a relationship between the phase transition temperature and the enthalpy of the crystallization of supercooled water. The melting temperature of the water in the membranes immersed in urea and NaCl 0–2 mol l^?1 aqueous solutions was also determined by d.s.c. analysis. The present study proposes a method for estimating the solubilities of urea and NaCl in both of the freezing and the non-freezing water using the melting point depression of the freezing water in the membranes immersed in the solute solution.     

Preparation of silk fibroin and polyallylamine composites

Composite films made of silk fibroin (SF) and polyallylamine (PAA) are prepared that contain various compositional ratios. These materials are analyzed to elucidate the resulting physical properties and to assess their potential toward advanced applications as industrial materials. The composite films are obtained from a SF and PAA binary system by dry casting from aqueous solution. These composite films exhibit excellent processability such as film forming capabilities, and the elongation at break is increased in the wet state. The differential scanning calorimetry (DSC) curves of the composites suggest that a mutual interaction takes place between the SF and PAA. This interaction is believed to occur because the endothermic peak, corresponding to the individual polymer, shifts with increasing SF content. The random coil conformation of the SF is present, regardless of the PAA blending, as confirmed by FTIR and DSC measurements. Additionally, living cells from Antheraea pernyi and Bombyx mori insect tissues are shown to grow effectively on the composite films. Maximum growth levels occur when the cultivation flask is coated with the material in SF/PAA ratios of 75:25 to 25:75. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1963–1970, 2002; DOI 10.1002/app.10491     

Photopolymerization of HEMA/DEGDMA hydrogels in solution

Photopolymerization is a widely used technique to synthesize polymers and hydrogels. The commonly used ultraviolet (UV)-curable mono-, di- or multifunctional vinylated monomers are often volatile, causing difficulty in kinetics analysis such as photo-differential scanning calorimetry (PhotoDSC). In this work, the DSC sample pan is chemically and physically modified such that the resin can be placed uniformly in the sample pan with minimum sample weight loss during measurement. This approach substantially improved experimental accuracy, which in turn provides a better understanding of the reaction kinetics of UV-curable polymers. Kinetic experiments were carried out for poly(2-hydroxyethyl methacrylate) (HEMA)-based hydrogels. The effects of light intensity and water concentration on the reaction kinetics and rheological change was investigated. It was found that increasing the light intensity enhances the polymerization, but too high an intensity slows down the reaction at the later stage. The addition of solvent and high light intensity facilitates the cyclization, delaying macrogelation. The viscosity rise of the resin system and the formed polymer size were also measured using a photorheometer and a particle size analyzer, respectively. The measured gel time, gel conversion and polymer size distribution agree with the kinetic analysis.