New block copolymers II. Synthesis and characterization of an ABA-type block copolymer

A new regular ABA-type triblock copolymer has been synthesized by polycondensation of the acid chloride of carboxy-terminated butadience-acrylonitrile rubber (CTBN) with hydroxyterminated polyethylene isophthalate (PEI) oligomer. This block copolymer was characterized by elemental (nitrogen) analysis, vapor pressure osmometry, viscometry, and IR and NMR spectroscopy. Quantitative estimation of block segments has been carried out by measuring the area under peaks assigned to various protons in the NMR spectrum of the polymer. NMR spectral analysis has been found to agree well with the nitrogen analysis of the polymer. The solubility and solution viscosity behavior of the polymer has also been studied.     

Orthogonal and fine lithographic structures attained from the next generation proton beam writing facility

A second generation proton beam writing (PBW) system has been built at the Centre for Ion Beam Applications at the National University of Singapore for fabrication of high aspect ratio 3D nano lithographic structures. System improvements and a few lithographic structures obtained with this facility are presented in this paper. Through accurate alignment of the magnetic quadrupole lenses and the electrostatic scanning system, orthogonal beam scanning has been achieved. The earlier constrain of limited beam scan area has been overcome by adopting a combination of beam and stage scanning as well as stitching. With these improvements smallest ever Ni structure of 65 nm in width has been fabricated using nickel electroplating on a proton beam written PMMA sample in the second generation PBW facility. Using this improved PBW facility, we have also demonstrated the fabrication of fine lithographic patterns with 19 nm line width and 60 nm spacing in 100 nm thick negative high resolution hydrogen silsesquioxane resist. Future possible system improvements leading to finer resolution will be discussed briefly.     

An SDP Primal-Dual Algorithm for Approximating the Lovász-Theta Function

The Lovász ?-function (Lovász in IEEE Trans. Inf. Theory, 25:1–7, 1979) of a graph G=(V,E) can be defined as the maximum of the sum of the entries of a positive semidefinite matrix X, whose trace Tr(X) equals 1, and X _ij =0 whenever {i,j}∈E. This function appears as a subroutine for many algorithms for graph problems such as maximum independent set and maximum clique. We apply Arora and Kale’s primal-dual method for SDP to design an algorithm to approximate the ?-function within an additive error of δ>0, which runs in time $O(\frac{\vartheta ^{2} n^{2}}{\delta^{2}} \log n \cdot M_{e})$ , where ?=?(G) and M _e =O(n ³) is the time for a matrix exponentiation operation. It follows that for perfect graphs G, our primal-dual method computes ?(G) exactly in time O(? ² n ⁵logn). Moreover, our techniques generalize to the weighted Lovász ?-function, and both the maximum independent set weight and the maximum clique weight for vertex weighted perfect graphs can be approximated within a factor of (1+?) in time O(? ^?2 n ⁵logn).     

Structural development in cycloolefin copolymers under uniaxial elongational flow

Development of structures in new cycloolefin copolymers (COCs) of ethylene–norbornene (E–NB) and ethylene–tetracyclododecene (E–TD) of different NB/TD compositions were investigated under uniaxial elongational flow. For E–NB copolymer, which has multiblock sequences, a shoulder in WAXD at 0.76 nm was evident besides its amorphous halo, and the relative intensity of the peak increased with increasing comonomer content (NB). The appearance of a new peak for E–TD copolymer, and a relatively higher intense peak for E–NB copolymer at the same position of 0.76 nm, indicated that local ordering of the segments occurred when the COC was subjected to uniaxial flow. A lower comonomer composition of elongated COC, at a constant Hencky strain rate, exhibited two T_g values, whereas a higher composition showed a single T_g. Both local ordering and segmentization occurred in low comonomer content COCs but only local ordering occurred in higher comonomer content COCs. Both the shear viscosity and roll processing experiments exhibited similar phenomena of segregation. A model is proposed to illustrate the structure of COC after uniaxial elongation/deformation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3421–3427, 2004     

Synthesis and characterization of poly(keto-amines). 2. Self-polycondensation of 4-methyl-3-aminophenacyl chloride and 2-methyl-4-aminophenacyl chloride

Poly(keto-amines) such as poly(4-methyl-3-iminophenacyls) and poly(2-methyl-4-iminophenacyls) were prepared by self-polycondensation of 4-methyl-3-aminophenacyl chloride and 2-methyl-4-aminophenacyl chloride under different experimental conditions. All the polymer samples were insoluble in common organic solvents. They were characterized by elemental analysis, IR spectral studies, estimation of M?_n by non-aqueous conductometric titration and study of thermal properties by DTA. The properties of P4M3IP and P2M4IP were compared with those of poly(4-iminophenacyls).     

Polybutylene terephthalate/high-density polyethylene alloys. I. Morphological studies

Polybutylene terephthalate (PBT) is a commercially successful thermoplastic polyester but has certain drawbacks such as low impact strength and low melt strength. An attempt has been made to modify the properties of PBT by blending it with polyolefin such as highdensity polyethylene (HDPE). Since PBT and HDPE are incompatible, an ionomer has been used as a compatibilizer to form an alloy. Alloys of PBT and HDPE with varying amounts (2-8%) of ionomer were prepared by melt blending. The ultimate mechanical properties improved significantly on the addition of the ionomer due to an increase in interfacial adhesion between PBT and HDPE. DSC studies show that the presence of ionomer facilitated the crystallization of PBT in the alloy. DMTA studies show that more of PBT (amorphous) is going in to the HDPE-rich phase in the presence of ionomer. The morphology of the alloys was studied using scanning electron microscopy (SEM), polarizing microscopy (PM), and small-angle light scattering (SALS). They showed improved dispersion of HDPE domains in PBT matrix with increasing ionomer content and change in the type of superstructure on adding the ionomer. It has been shown that an alloy of PBT and HDPE with improved mechanical properties and homogeneous morphology can be made with use of ionomer as a compatibilizer. Such alloys are cost effective and can find use in several engineering applications.     

Corrosion of 2205 duplex stainless steel in chloride medium containing sulfate-reducing bacteria

Sulfate-reducing bacteria (SRB) play significant role in the corrosion of stainless steels exposed to marine and soil environment. Sulfate reduction by bacterial species results in the production of H₂S, which can significantly influence the anodic and cathodic processes and ultimately enhances the corrosion of materials. In the present study, 2205 type duplex stainless steel (DSS) coupons in solution-annealed condition were exposed to chloride medium containing SRB species, Desulfovibrio desulfuricans, for 40 days and examined by microscopy. Etching of the duplex structure, pitting as well as crevice attack were noticed. Similar results were obtained by microscopic studies with coupons exposed for 14 days in medium containing SRB followed by anodic polarization. SEM studies, of crevices observed after anodic polarization, indicated that the attack was initiated at the grain boundaries and slowly encroached into austenite grains. The initiation of attack was also evident from AFM studies of coupon exposed under freely corroding conditions for 7 days. ESCA studies reveal that under anaerobic conditions of SRB growth sulfidation of passive film occurs. The modified passive film found to depolarize the cathodic reactions. The nature and mechanism of SRB attack on DSS and possibility of detection at early stages were discussed.     

Electrical Conduction in Nano-Structured La0.9Sr0.1Al0.85Co0.05Mg0.1O3 Perovskite Oxide

Nanocrystalline La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ oxide powder was synthesized by a citrate–nitrate auto-ignition process and characterized by thermal analysis, X-ray diffraction, and impedance spectroscopy measurements. Nanocrystalline (50–100 nm) powder with perovskite structure could be produced at 900°C by this process. The powder could be sintered to a density more than 96% of the theoretical density at 1550°C. Impedance measurements on the sintered samples unequivocally established the potential of this process in developing nanostructured lanthanum aluminate-based oxides. The sintered La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ sample exhibited a conductivity of 2.40 × 10⁻² S/cm in air at 1000°C compared with 4.9 × 10⁻³ S/cm exhibited by La_0.9Sr_0.1Al_0.85Mg_0.15O₃.     

Studies on polyblends of poly(vinyl chloride) and acrylonitrile-butadiene-styrene terpolymer

Blends of poly (vinyl chloride) (PVC) and acrylonitrile-butadiene styrene (ABS) terpolymer were prepared in different ratios by a melt blending technique. ABS containing three different levels of rubber content were used. A quantitative assessment of ABS in PVC/ABS blends has been shown by infrared studies. ABS content has been shown as the presence of the characteristic acrylonitrile peak. Differential scanning calorimetry (DSC) studies have been carried out to study the glass transition (T_g) behavior of the blends. Two T_g values corresponding to PVC and styrene-acrylonitrile (SAN) copolymer have been observed. Thermogravimetric analysis (TGA) reveals a significant improvement in thermal stability of these blends as compared to PVC. Mechanical properties show a significant increase in the impact strength which is related to rubber content of the ABS used. Morphological studies have been carried out by scanning electron microscopy which support the observation that an increase in rubber content results in greater ductility.