Synthesis and characterization of in situ polymerized segmented thermoplastic elastomeric polyurethane/layered silicate clay nanocomposites

Nanocomposites based on thermoplastic elastomeric polyurethane (TPU) and layered silicate clay were prepared by in situ synthesis. The properties of nanocomposites of TPU with unmodified clay were compared with that of organically modified clay. The nanocomposites of the TPU and organomodified clay showed better dispersion and exhibited superior properties. Exfoliation of the clay layers was observed at low organoclay contents, whereas an intercalated morphology was observed at higher clay contents. As one of major purposes of this study, the effect of the silicate layers in the nanocomposites on the order–disorder transition temperature (T_ODT) of the TPU was evaluated from the intensity change of the hydrogen‐bonded and free carbonyl stretching peaks and from the peak position change of the N? H bending peak. The presence of the organoclay increased T_ODT by approximately 10°C, which indicated improved stability in the phase‐separated domain structure. The layered silicate clay caused a tremendous improvement in the stiffness of the TPU; meanwhile, a reduction in the ultimate elongation was observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3048–3055, 2006     

Molecular dynamics and thermal analysis study of anomalous thermodynamic behavior of poly (ether imide)/polycarbonate blends

Molecular dynamics simulation used to study the binary polymer blend of poly (ether imide) (PEI) and polycarbonate (PC) showed that these polymer blends are immiscible. The Flory-Huggins interaction parameter, χ, calculated from simulation reached a minimum value at 80 wt% PEI. The simulation results showed that the concentration dependence of χ was mainly due to electrostatic interaction and van der Waals force. The simulation results were supported by differential scanning calorimetry (DSC) measurements. The DSC measurements showed that there are two distinct glass transition temperatures for all the blends' concentrations. However, at 80wt % PEI, the T_g of PEI-rich phase reached a minimum while that of the PC-rich phase was comparable to its pure form indicating that there is some partial miscibility of PC in the PEI rich phase, but no PEI is incorporated in the PC rich phase. From simulations, the χ versus concentration plot shows the same trend as the experimentally measured glass transition temperature versus concentration plot.     

Structure of poly(vinyl alcohol)-iodine complex formed in the amorphous phase of poly(vinyl alcohol) films

The effect of syndiotactivity of poly(vinyl alcohol) (PVA) both on the formation and thermal stability of the complex formed in the amorphous phase of PVA films is investigated, and then a model of the complex is presented. The amount of the complex formed in syndiotacticity-rich PVA is much larger than that formed in atactic PVA under a given iodine-soaking condition, and the former complex has a higher thermal stability in the soaking solution than the latter. The complex formed in the amorphous phase is proposed to have such a structure as that in which a linear polyiodine I₅^? or I₅^? with a 3.1 A? periodicity is enveloped by four PVA segments of syndiotactic configuration with extended conformation. In this model, these four PVA chains participating in a complex are supposed to be fixed by interchain hydrogen bonds. The observed X-ray meridional intensity curve of iodinated PVA film can be explained by a series of two I₅^?. © 1993 John Wiley & Sons, Inc.     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

Durable antimicrobial treatment of cotton fabrics using N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride and polycarboxylic acids

N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), a water‐soluble chitosan quaternary ammonium derivative, was used as an antimicrobial agent for cotton fabrics. HTCC has a lower minimum inhibition concentration (MIC) against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli compared to that of chitosan; however, the imparted antimicrobial activity is lost on laundering. Thus crosslinking agents were utilized to obtain a durable antimicrobial treatment by immobilizing HTCC. Several crosslinkers such as dimethyloldihydroxyethylene urea (DMDHEU), butanetetracarboxylic acid (BTCA), and citric acid (CA) were used with HTCC to improve the laundering durability of HTCC treatment by covalent bond formation between the crosslinker, HTCC and cellulose. The polycarboxylic acid treatment was superior to the DMDHEU treatment in terms of prolonged antimicrobial activity of the treated cotton after successive laundering. Also, the cotton treated with HTCC and BTCA showed improved durable press properties without excessive deterioration in mechanical strength or whiteness when compared to the citric acid treatment. With the addition of only 0.1% HTCC to BTCA solutions, the treated fabrics showed durable antimicrobial activity up to 20 laundering cycles. The wrinkle recovery angle and strength retention of the treated fabrics were not adversely affected with the addition of HTCC. Therefore, BTCA can be used with HTCC in one bath to impart durability of antimicrobial activity along with durable press properties to cotton fabric. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1567–1572, 2003     

Structure and properties of poly(vinyl alcohol)–iodine complex formed in the crystal phase of poly(vinyl alcohol) films

The structure and optical properties of the complex formed in the crystal phase of PVA that is caused by soaking at very high iodine concentration are investigated. In the resonance Raman spectra of lightly and heavily iodinated specimens, two Raman shifts appeared at 109 and 161 cm^?1. The 109 cm^?1 peak due to the I mode was much stronger than the 161 cm^?1 peak in a heavily iodinated specimen, whereas the peak was comparable with the 161 cm^?1 peak in a lightly iodinated specimen. The complex formed in the crystal phase is identified as the I mode complex. It has an averaged iodine–iodine distance of 3.2 Å, which is different from the 3.08 Å of the I mode complex formed in the amorphous phase. The effect of KI concentration in the soaking solution on the formation of the complex is also examined. The increased KI concentration in the soaking solutions at a fixed iodine concentration increases the amount of the complex formed in the crystal phase. The change in the hydrogen-bonding state in the crystal phase with the complex formation can be evidenced by IR and NMR. © 1994 John Wiley & Sons, Inc.     

Fabrication of a gradient refractive index preform using laminar shear mixing

A gradient refractive index rod was successfully prepared by a new fabrication method using laminar shear mixing, and a graded index polymer optical fiber that satisfied IEEE1394b was obtained from the method. To fabricate the gradient refractive index rod, a liquid monomer mixture with a relatively low refractive index was placed in a prepared cylindrical glass reactor and a transparent polymer rod with a higher refractive index was introduced at the center of the reactor. The reactor and the polymer rod were then rotated concurrently with a small rotating speed difference to generate a Couette flow in the liquid phase. The centrifugal force generated by rotation and the polymer diffusion into the liquid monomer mixture developed a graded concentration profile in a radial direction. The Couette flow could reduce the concentration fluctuation in a tangential direction. In addition, the graded index profile could be controlled by the copolymer composition of the rod and its diameter. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1100–1104, 2005     

Modeling and economic analysis of CO<Subscript>2</Subscript> separation process with hollow fiber membrane modules

The main purpose of the study was to develop a model using ASPEN and Excel simulation method to establish optimum CO₂ separation process utilizing hollow fiber membrane modules to treat exhaust gas from LNG combustion. During the simulation, optimum conditions of each CO₂ separation scenario were determined while operating parameters of CO₂ separation process were varied. The characteristics of hollow fibers membrane were assigned as 60 GPU of permeability and 25 of selectivity for the simulation. The simulation results illustrated that 4 stage connection of membrane module is required in order to achieve over 99% of CO₂ purity and 90% of recovery rate. The resulted optimum design and operation parameters throughout the simulation were also correlated with the experimental data from the actual CO₂ separation facility which has a capacity of 1,000 Nm³/day located in the Korea Research Institute of Chemical Technology. Throughout the simulation, the operating parameters of minimum energy consumption were evaluated. Economic analysis of pilot scale of CO₂ separation plant was done with the comparison of energy cost of CO₂ recovery and equipment cost of the plant based on the simulation model. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Physical and electroresponsive characteristics of the intercalated styrene‐acrylonitrile copolymer/clay nanocomposite under applied electric fields

Styrene‐acrylonitrile copolymer (SAN)/clay nanocomposites were synthesized through an emulsion copolymerization of styrene and acrylonitrile in the presence of sodium montmorillonite, and their physical properties and electroresponsiveness under an applied electric field were characterized. Thermogravimetric analysis (TGA) showed that the thermal stability of the synthesized polymer was sustained. X‐ray diffraction (XRD) analysis confirmed the insertion of SAN into the interlayers of clay, whose separation consequently increased, as compared to those of the pristine clay. Transmission electron microscopy (TEM) was used to observe the suspended state of clay. Dry‐base electrorheological (ER) fluids were prepared by mixing intercalated SAN nanocomposite particles into silicone oil. Typical ER behavior, i.e., enhancement of shear and yield stresses in the presence of an applied electric field, was observed using a rotational rheometer equipped with a high‐voltage generator. A universal yield stress scaling equation was also found to fit our experimental data well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 821–827, 2003     

Electromechanical behavior of hybrid carbon/glass fiber composites with tension and bending

To understand the smart (i.e., good memory) characteristics of hybrid composites of carbon fibers (CFs) and glass fibers (GFs) with epoxy resin as a matrix, the changes in the electrical resistance of composites with tension and on bending were investigated. The electrical resistance behavior of composites under tension changed with the composition of the CF/GF, as well as with the applied strain. The fractional electrical resistance increased slowly with increasing strain within a relatively low strain region. However, with further loading it increased stepwise with the strain according to the fracture of the CF layers. The strain sensitivity of the samples increased with increasing CF weight percentage, and the samples incorporating more than 40 wt % CF showed a strain sensitivity higher than 1.54 for a single CF. The changes in the fractional electrical resistance with bending were not so dominant as those with tension. This difference was attributed to the action of two cancelling effects, which are the increasing and decreasing fractional electrical resistance due to tension and compression with bending, respectively. On recovery from a large applied bending, the fractional electrical resistance decreased slowly with unloading because of the increase of contacts between the fibers that resulted from the reorganization of ruptured CFs during the recovery. Even the composites incorporating a relatively small CF content showed an irreversible electrical resistance with both tension and bending. However, the strain sensitivity being larger with tension than with bending is ascribed to the difference in their mechanical behaviors. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2447–2453, 2002