Novel,organosoluble, light‐colored fluorinated polyimides based on 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl or 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl

Two series of fluorinated polyimides were prepared from 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( 2 ) and 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl ( 4 ) with various aromatic dianhydrides via a conventional, two‐step procedure that included a ring‐opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. The inherent viscosities of the polyimides ranged from 0.54 to 0.73 and 0.19 to 0.36 dL/g, respectively. All the fluorinated polyimides were soluble in many polar organic solvents, such as N,N‐dimethylacetamide and N‐methylpyrrolidone, and afforded transparent and light‐colored films via solution‐casting. These polyimides showed glass‐transition temperatures in the ranges of 222–280 and 257–351 °C by DSC, softening temperatures in the range of 264–301 °C by thermomechanical analysis, and a decomposition temperature for 10% weight loss above 520 °C both in nitrogen and air atmospheres. The polyimides had low moisture absorptions of 0.23–0.58%, low dielectric constants of 2.84–3.61 at 10 kHz, and an ultraviolet–visible absorption cutoff wavelength at 351–434 nm. Copolyimides derived from the same dianhydrides with an equimolar mixture of 4,4′‐oxydianiline and diamine 2 or 4 were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2416–2431, 2004     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

Completely biodegradable composites of poly(propylene carbonate) and short,lignocellulose fiber Hildegardia populifolia

The composites of biodegradable poly(propylene carbonate) (PPC) reinforced with short Hildegardia populifolia natural fiber were prepared by melt mixing followed by compression molding. The mechanical properties, thermal properties, and morphologies of the composites were studied via static and dynamic mechanical measurements, thermogravimetric analysis, and scanning electron microscopy (SEM) techniques, respectively. Static tensile tests showed that the stiffness and tensile strength of the composites increased with an increasing fiber content. However, the elongation at break and the energy to break decreased dramatically with the addition of short fiber. The relationship between the experimental results and the compatibility or interaction between the PPC matrix and fiber was correlated. SEM observations indicated good interfacial contact between the short fiber and PPC matrix. Thermogravimetric analysis revealed that the introduction of short Hildegardia populifolia fiber led to a slightly improved thermooxidative stability of PPC. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 666–675, 2004     

Reversible nonlinear conduction in high‐density polyethylene/acetylene carbon black composites at various ambient temperatures

The reversible nonlinear conduction (RNC) in of high‐density polyethylene/acetylene carbon black composites with different degrees of crosslinking was studied above room temperature and below the melting point of high‐density polyethylene (HDPE). The experimental current density‐electric field strength curves can be overlapped onto a master curve, suggesting that the microscopic mechanisms for the appearance of RNC exist regardless of the ambient temperature and the crosslinking degree of the HDPE matrix. The relationship between the crossover current density and the linear conductivity can be explained in the framework of the dynamic random‐resistor‐network model. According to these results, two electron‐tunneling models are suggested to interpret the microscopic conduction behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1212–1217, 2004     

Combined effects of clay modifications and compatibilizers on the formation and physical properties of melt‐mixed polypropylene/clay nanocomposites

The melt mixing technique was used to prepare various polypropylene (PP)‐based (nano)composites. Two commercial organoclays (denoted 20A and 30B) served as the fillers for the PP matrix, and two different maleated (so‐called) compatibilizers (denoted PP‐MA and SMA) were employed as the third component. The results from X‐ray diffraction (XRD) and transmission electron microscope (TEM) experiments revealed that 190 °C was an adequate temperature for preparing the nanocomposites. Nanocomposites were achieved only if specific pairs of organoclay and compatibilizer were simultaneously incorporated in the PP matrix. For example, PP/20A(5 wt %)/PP‐MA(10 wt %) and PP/30B(5 wt %)/SMA(5 wt %) composites exhibited nanoscaled dispersion of 20A or 30B in the PP matrix. Differential scanning calorimetry (DSC) results indicated that the organoclays served as nucleation agents for the PP matrix. Generally, their nucleation effectiveness increased with the addition of compatibilizers. The thermal stability enhancement of PP after adding 20A was confirmed with thermogravimetric analysis (TGA). The enhancement became more evident as a suitable compatibilizer was further added. However, for the 30B‐included composites, thermal stability enhancement was not evident. The dynamic mechanical properties (i.e., storage modulus and loss modulus) of PP increased as the nanocomposites were formed; the properties increment corresponded to the organoclay dispersion status in the matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4139–4150, 2004     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Viscosity,particle size distribution,and structural investigation of tetramethyloxysilane/2‐hydroxyethyl methacrylate sols during the sol–gel process with acid and base catalysts

The tetramethoxysilane (TMOS)/2‐hydroxylethyl methacrylate (HEMA) hybrid gels were synthesized with acid and base catalysts, via the in situ polymerization of HEMA, with and without the cosolvent methanol. With methanol in the TMOS/HEMA sol, the enhanced esterification and depolymerization reactions of the silanols resulted in a slower growth of silica particles. The silica particles that were synthesized with an acid catalyst were less than 40 nm. The thermal resistance of the poly(2‐hydroxyethyl methacrylate) (PHEMA) chains was enhanced by the addition of colloidal silica. The Fourier transform infrared characterizations and the exothermal peaks on the differential scanning calorimetry traces of these hybrid gels indicated chemical hybridization occurring as a result of condensation of the colloid silica and PHEMA at higher temperatures. Hence, the residual weight content of the hybrid gel after its synthesis with the base catalyst was even higher than the content of TMOS in the hybrid sol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3476–3486, 2004     

Control of self‐organized low‐dimensional morphology in poly(styrene‐b‐4vinylpyridine)/polystyrene blend thin films

The surface morphologies of poly(styrene‐b‐4vinylpyridine) (PS‐b‐P4VP) diblock copolymer and homopolystyrene (hPS) binary blend thin films were investigated by atomic force microscopy as a function of total volume fraction of PS (?_PS) in the mixture. It was found that when hPS was added into symmetric PS‐b‐P4VP diblock copolymers, the surface morphology of this diblock copolymer was changed to a certain degree. With ?_PS increasing at first, hPS was solubilized into the corresponding domains of block copolymer and formed cylinders. Moreover, the more solubilized the hPS, the more cylinders exist. However, when the limit was reached, excessive hPS tended to separate from the domains independently instead of solubilizing into the corresponding domains any longer, that is, a macrophase separation occurred. A model describing transitions of these morphologies with an increase in ?_PS is proposed. The effect of composition on the phase morphology of blend films when graphite is used as a substrate is also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3496–3504, 2004