Adhesion property of novel polyimides with 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride

Novel polyimides were synthesized from 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride (6FPPMDA) by a conventional two‐step process: the preparation of poly(amic acid) followed by solution imidization via refluxing in p‐chlorophenol. The diamines used for polyimide synthesis included bis(3‐aminophenyl)‐3,5‐bis(trifluoromethyl)phenyl phosphine oxide, bis(3‐aminophenyl)‐4‐trifluoromethylphenyl phosphine oxide, and bis(3‐aminophenyl)phenyl phosphine oxide. The synthesized polyimides were designed to have a molecular weight of 20,000 g/mol by off‐stoichiometry and were characterized by Fourier transform infrared, NMR, differential scanning calorimetry, and thermogravimetric analysis. In addition, their intrinsic viscosity, solubility, water absorption, and coefficient of thermal expansion (CTE) were also measured. The adhesion properties of the polyimides were evaluated via a T‐peel test with bare and silane/Cr‐coated Cu foils, and the failure surfaces were investigated with scanning electron microscopy. The 6FPPMDA‐based polyimides exhibited high glass‐transition temperatures (280–299°C), good thermal stability (>530°C in air), low water absorption (1.46–2.16 wt %), and fairly low CTEs (32–40 ppm/°C), in addition to good adhesion properties (83–88 g/mm) with silane/Cr‐coated Cu foils. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1801–1809, 2005     

Polymer gel electrolytes prepared from P(EG‐co‐PG) and their nanocomposites using organically modified montmorillonite

Polymer gel electrolytes were prepared by thermal crosslinking reaction of a series of acrylic end‐capped poly(ethylene glycol) and poly(propylene glycol) [P(EG‐co‐PG)] having various geometries and molecular weights. Acrylic end‐capped prepolymers were prepared by the esterification of low molecular weight (M_n: 1900–5000) P(EG‐co‐PG) with acrylic acid. The linear increase in the ionic conductivity of polymer gel electrolyte films was observed with increasing temperature. The increase in the conductivity was also monitored by increasing the molecular weight of precursor polymer. Nanocomposite electrolytes were prepared by the addition of 5 wt % of organically modified layered silicate (montmorillonite) into the gel polymer electrolytes. The enhancement of the ionic conductivity as well as mechanical properties was observed in the nanocomposite systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 894–899, 2004     

Prepreg aging in relation to tack

Thermoanalytical measurements and tack tests were both performed using a commercially available carbon fiber/epoxy prepreg system (Hercules 3501–6) to examine changes caused by aging as they affect handling and processability of thermosetting matrix-based composites. Combining these techniques, a relationship between prepreg bulk and surface characteristics in relation to aging was investigated. Isothermal kinetic studies at low temperatures showed maximum conversions (α_m) that increased with increasing cure temperatures. In addition, a linear relationship between glass transition temperatures (T_g) and conversions (α) was observed regardless of aging (or cure) temperatures. Energy of separation of prepreg stacks, which may be viewed as a measure of prepreg tack, showed a maximum value at a specific temperature. The maximum energy of separation was observed in the temperature range of 20–25°C above the glass transition temperature for a given sample. However, the maximum energy of separation values decreased with increasing aging times (or conversions), implying that prepreg tack was a viscoelastic property rather than a viscous property of the resin matrix in the prepreg.     

Microstructural changes in homopolymers and polymer blends induced by elastic strain pulverization

A novel polymer processing technique known as elastic strain pulverization (ESP) involves the simultaneous effects of high pressure and shear deformation to pulverize polymers. Homopolymers and blends of commercially important postconsumer plastics, including high-density and low-density polyethylene (HDPE, LDPE), polypropylene (PP), and poly styrene (PS) are studied by several characterization techniques to determine the effects of ESP on the microstructure. Electron spin resonance spectroscopy confirms that free radicals are generated by the mechanical rupture of main chain carbon bonds during pulverization by ESP. The possibility of these free radicals terminating by heterogeneous combination to form compatibilizing block or graft copolymers in coprocessed polymer blends establishes the potential of ESP in commingled plastics recycling. Differential scanning calorimetry (DSC) and polarized light microscopy of homopolymers and blends indicate that crystalline structure is drastically altered by ESP processing. Spherulite size reduction is also observed in both crystalline/crystalline and crystalline/amorphous blends after ESP. These results are consistent with homogenization that may be due to the formation of compatibilizing copolymers by heterogeneous macroradical combination. © 1995 John Wiley & Sons, Inc.     

Comparison of liquid-phase and methanol-swelling crosslinking processes of polyimide dense membrane for CO2/CH4 separation

To overcome the plasticization effect in polyimide membranes, many researchers have proposed crosslinking method. This can reduce an inter-segmental mobility by tightening and rigidifying the polymer chains. However, it is difficult to modify the whole polymer chains throughout the membrane because the reaction can be hindered by the diffusion rate of the crosslinker. In particular, it is hard for bulky crosslinker to penetrate a dense membrane with a small d-spacing. This study investigated the effect of crosslinking a dense Matrimid membrane with p-phenylenediamine (p-PDA) via two different crosslinking methods (i.e., methanol-swelling crosslinking process [M-SCP] and liquid-phase crosslinking process [L-PCP]). Most of the crosslinking reaction in M-SCP occurs on the membrane surface due to difficulty in penetration of the bulky p-PDA into the Matrimid dense membrane. In contrast, the L-PCP allows uniform crosslinking across the membrane. The membranes crosslinked using L-PCP showed excellent chemical resistance. Furthermore, the plasticization phenomenon was not observed in the membranes crosslinked using L-PCP with p-PDA more than 15%. Meanwhile, the membrane crosslinked using M-SCP exhibited poor plasticization and chemical resistance properties. These results showed that the L-PCP method can be more effective for the crosslinking of dense membrane to deliver both high plasticization and chemical resistance.     

A study on corrosion resistance characteristics of PVD Cr-N coated steels by electrochemical method

The corrosion behavior of Cr-N coated steels with different phases (-Cr, CrN and Cr₂N) deposited by cathodic arc deposition on AISI H13 steel was investigated in a 3.5% NaCl solution at ambient temperature. Potentiodynamic polarization tests, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were the techniques applied to characterize the corrosion behavior. It was found that the CrN coating had a lower current density from potentiodynamic polarization tests than others. The porosity, corresponding to the ratio of the polarization resistance of the uncoated and the coated substrate, was higher in the Cr₂N coating than in the other Cr-N coated steels. EIS measurements showed, for most of the Cr-N coated steels, that the Bode plot presented two time constants. Also, the Cr₂N coating represented the characteristic of Warburg behavior after 72 h of immersion. The coating morphologies were examined in planar view and cross-section by SEM analysis and the results were compared with those of the electrochemical measurement. The CrN coating had a dense, columnar grain-sized microstructure with minor intergranular porosity. From the above results, it is concluded that the CrN coating provided a better corrosion protection than the other Cr-N coated steels.     

Nitrogen removal using recycled polystyrene bottles as biofilm media

The performance of an attached growth wastewater treatment process was investigated in an effort to improve nitrogen removal efficiency. Recycled Yakult (lactic acid fermentation drink) bottles made of polystyrene were used as a biofilm media. The use of Yakult bottles as a biofilm media has been attempted by numerous researchers in Japan for the removal of solids and organics. However, these studies focused only on the removal of solids and organics. This study extended their application to the removal of nitrogen for domestic sewage treatment. Yakult media was placed in a reactor with 70% apparent reactor volume in a conventional A/O process. The bottom of the Yakult media was removed, and randomly filled Yakult media were effectively able to reduce the flow in tanks, resulting in an increase in the contact time between pollutants and microorganisms. With higher HRT, the nitrogen removal efficiency was increased by up to 83% with 12 hr of HRT. Nitrification appeared to be the limiting factor of nitrogen removal at an HRT that is less than 12 hr, indicating that the Yakult process requires more retention time to achieve nitrification compared to other biofilm processes. The removal efficiencies of organics and solids were high regardless of the change of operational parameters. This article is based on a presentation in “The 7th Korea-China Workshop On Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24–27, 2003.     

Effects of anodizing voltage on the anodized and hydrothermally treated titanium surface

Anodic oxidation is the process of creating a titanium oxide layer with various defects more dense and stable. In this study, a dense, stable and porous oxide layer was formed using anodic spark oxidation on pure titanium surface and hydroxyapatite crystals were formed on its surface via a hydrothermal treatment. A mixture of 0.02M−GP (Glycerolphosphate disodium salt) and 0.2M-CA (Calcium acetate) was used as an electrolyte. By increasing the anodizing voltage to 220, 260, 300, and 360 V, the effects of the anodizing voltage were examined by evaluating the film properties after anodization and a hydrothermal treatment. Breakdown occurred around 230 V. As the voltage increased after breakdown, the pore size increased. After the hydrothermal treatment, the amount of HA crystal precipitation was also increased as the voltage increased. The mean surface roughness (Ra) of the anodizing surface was also increased as the voltage increased. The Ra value was larger in the hydrothermally treated group compared with the group treated with anodization as a result of the HA crystals present on the surface after the hydrothermal treatment. Corrosion resistance of the surface modified by anodization was significantly increased in a saline solution compared to that for the non-treated group; this increased further after the hydrothermal treatment. These increases were most likely due to a thick stable oxide layer formed through anodization. Thus, it is believed that titanium with its surface modified through anodic spark oxidation would be a suitable biomaterial due to its corrosion resistance and biocompatibility.     

Discharge characteristics of lead dioxide electrode prepared with cementation lead oxide

Lead acid batteries have had restricted applications because of relatively low energy density below 50Wh/kg. Many efforts have achieved lighter battery components such as separators, connections and containers etc. Thus, the most important problem of the lead acid battery is to improve the low capacity of the active material in the positive electrode. The purpose of this study is to improve the utilization of the active material in the lead dioxide electrode for the lead acid battery through the production of lead oxide with better physicochemical characteristics through cementation. A cementation reaction was performed in 1.0wt.%HCl solution using pure magnesium plate as the reductant. We investigated the utilization of the active material and discharge characteristics of the positive electrode with a current density ranging from 3.4 to 108.8mAcm⁻². As a result, the active material utilization was about 72% at 3.48 mAcm⁻² and increased with decreasing current density. The discharge characteristics according to current density are especially very good at high current density     

Microstructure and mechanical property of irradiated Zr−2.5Nb pressure tube in Wolsong unit-1

With the aim of assessing the degradation of Zr−2.5Nb pressure tubes operating in the Wolsong unit-1 nuclear power plant, characterization tests are being conducted on irradiated Zr−2.5Nb tubes removed after 10-year operation. The examined tube had been exposed to temperatures ranging from 264 to 306°C and a neutron fluence of 8.9×10²¹ n/cm² (E>1 MeV) at the maximum. Tensile tests were carried out at temperatures ranging from RT to 300°C. The density of a-type and c-type dislocations was examined on the irradiated Zr-2.5Nb tube using a transmission electron microscope. Neutron irradiation up to 8.9×10²¹ n/cm² (E>1 MeV) yielded an increase in a-type dislocation density of the Zr−2.5Nb pressure tube to 7.5×10¹⁴ m⁻², which was highest at the inlet of the tube exposed to the low temperature of 275°C. In contranst, the c-component dislocation density did not change with irradiation, keeping an initial dislocation density of 0.8×10¹⁴ m⁻² over the whole length of the tube. As expected, the neutron irradiation increased mechanical strength by about 17–26% in the transverse direction and by 34–39% in the longitudinal direction compared to that of the unirradiated tube at 300°C. The change in the mechanical properties with irradiation is discussed in association with the microstructural change as a function of temperature and neutron fluence.